TW200305582A - Incorporable photoinitiator - Google Patents

Abstract

Compounds of formula I, wherein Y is, for example, C3-C12alkylene, butenylene, butynylene, or C4-C12alkylene interrupted one or more times by non-consecutive -O- or -NR2-; R1 is a reactive group selected from OH, SH, NR3R4, -(CO)-OH, -(CO)- NH2, SO3H, -C(R5)=CR6R7, oxiranyl, -O-(CO)-NH-R8-NCO and -O-(CO)- R9-(CO)-X; R2 is hydrogen, C1-C4 alkyl or C2-C4 hydroxyalkyl; R3 and R4 are each independently of the other hydrogen, C1-C4alkyl or C2-C4hydroxyalkyl; R5, R6 and R7 are each independently of the others hydrogen or methyl; R8 is, for example, linear or branched C4-C12alkylene, or phenylene; R9 is, for example, linear or branched C1-C16 alkylene, -CH=CH-, - CH=CH-CH2-, C6-cycloalkylene, phenylene or naphthylene; and X, X1 and X2 are each independently of the others OH, Cl, OCH3 or OC2H5; are suitable as photoinitiators that can be incorporated in a formulation to be cured.

Description

200305582 发明 Description of the invention (The description of the invention shall state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings are briefly explained) Technical field of the invention of the genus L 3 Type light initiator, which can be incorporated into the composition to be polymerized by its special substituent. I: Prior art 3 5 Phenylglyoxylic acid is known as a photoinitiator and is described in, for example, US 4 038 164, US 4 475 999, and US 4 024 297. Compounds having diphenylglyoxylate functionality in one molecule are known from, for example, US 6 048 660 and WO 00/56822. Phenylglyoxylic acid derivatives providing acrylate groups are disclosed in US 3 930 868, US 4 308 394 and US 4 10 279 718. In this technology, a low volatility reactive photoinitiator is required. In addition to excellent starter properties and good dark-storage stability of the formula mixed with it, it is also provided for composite compositions. A wide range of formulations, such as mixtures of components that can be thermally and photochemically cured, 15 which can also be incorporated into these formulations by rapid migration for these photoinitiators or their photolysis products. It has now been found that certain phenylglyoxylates are particularly suitable as photoinitiators with low volatility. These esters become compounds that are strongly incorporated in the coating during the polymerization reaction, and migration of the initiator is avoided. 20 [Summary of the Invention] Therefore, the present invention relates to the photoinitiator compound 0 of the incorporation of the chemical formula I (continued page of the invention description page, please note and use the continued page) ac γΟ-Υ-Κ

II ⑴, where 0Y is CVC ^ 2 alkylene, butenyl, butynyl, or cVCi2 alkylene interrupted one or more times with non-continuous 0- or -NR2. BenQ, Cyclohexyl,

5 Ri is selected from 0H, SH, NR3R4,-(CO) -OH,-(CO) -NH2, S03H, -C (R5) = CR6R7, ethylene oxide, -0- (c〇) -NH -R8-NCO and (CO) -R9- (CO) -X reactive groups; hydrogen, alkyl or c2-c4 hydroxyalkyl; each of R3 and R4 is individually hydrogen, CVC4 alkyl or c2-c4 Hydroxyalkyl; 10 r5, r6 and r7 each is hydrogen or methyl; r8 is linear or branched c4-c12 alkylene, phenylene, fluorenyl-phenylene, cyclohexanediyl , Isophorone diyl, ~ 〇-ch ^ O ~, -〇-chhQ-,

15 ^ ch2) 6 ~ n-c-n-c-n- (ch2) 6-n = c = o: (ch2) 6 0 Continued pages (If the description page of the invention is not enough, please note and use the continued page) 200305582 玖, Description of the invention

ίϊ N

ίϊ N ^ CH2) 6 ~ N ~ CNCN-(CH2) rN-C- (OCH2CH2) jO-CC- · ^^ (ch2) 6 〇 卜 / (ch2) 6—-(CH2) rN > = 0 tN, 0 (CH2) rN = C = 0

Vn / CH2) 6_-(CH2) g-N ^ = 0 ii

O or 0 (CH2) rN—C— (OCH2CH2) 2〇-C-C- o

X • (CWrN ^ N— (CH2) r

If o R9 is a linear or branched CVCidt alkyl group, -CH = C: Il · _〇Ή = (: Ιί »CH2_, cv, cycloalkylene, phenylene, naphthyl, norbornaline-5, 6-diyl, CO-X, co-x, ~ CH—C—or CH, —CHr-C— · and 2 II '& CH2 X, Xi, and X2 each is OH, ci, och3 Or 0c2H5. 10 The properties of the compound of formula I are the R! Group reactive group. The "reactive group" in this context needs to understand that it can react with the formulation to be polymerized and is therefore stable in this formulation. The base of the substance. The migration of the photoinitiator is therefore continued on the 0th page (when the description page of the invention is insufficient, please note and use the continued page) 200305582 玖, the description of the invention is reduced. And is methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, or third butyl. C2_C4 hydroxyalkyl is a c2_C4 alkyl substituted with one or more 0H groups, Alkyl is as defined above and has a corresponding number of carbon atoms. Examples are hydroxyethyl, dihydroxypropyl, hydroxypropyl, and dihydroxyethyl, especially hydroxyethyl 0 10

CrCi2 alkylene is linear or branched alkylene, for example, propylene, isopropyl, n-butyl, second butyl, third butyl, phenyl, hexyl, heptyl , Octyl, octyl, octyl, decyl, decyl—CH—I 5 0 ”Η23 —〒H-CH2-, —-CH- (CH2) 2- 5 ch3 ch3 〒h- (ch2) 3-, _ (: ((: Ιί3) 2-(: ΙΙ2- or ch3 c2h5 -CH-C-CH2-ch3 o C4_C12 discontinuous one or more times with non-continuous -0- or -NR ^ Alkyl produces such as -CH2CH2-0-CH2CH2-,-[CH2CH20] y- (where y = 2_9), 15-(CH2CH2〇) 5CH2CH2-, ~ ^^ 2 ^ CH (C) i3) -〇-Cli2 -C} i (C ¥ L3)-. The structural unit of CH2CH2- (NR2) -CH2CH2-. 0 Ethylene oxide-c-ch2 Η 0 c6-cycloalkylene system one or one. Preferred chemical formula The compound of I is 13 of which is the next page (if the description page of the invention is not enough, please note and use the next page) 9 200305582 玖, Description of the invention Y series -CH2-CH (CH3K orthopropyl, -CH2C (CH3) 2CH2- , Hexyl,-(: Η2 (: Η2-0 _ (: Η2 (: Η2 _,-(ch2ch2-o) 2ch2ch2-,

Leaf or

Compounds of formula I whose center is OH are of particular interest. Special enthusiasts are compounds in which h is OH and Y is _CH2CH2-0-CH2CH2-. I also like (more specifically) the incorporable photoinitiators of Chemical Formula I in which Y is a C4-C12 elongation group with non-continuous -0- intermittent one or more times;

Ri is OH, ethylene oxide and -0- (c〇) -NH-R8-NCO reactive 10 groups; and r8 is

^ οη2) 6 ~ ν · ~ 〇 · ν-ο-ν-(〇η2) γν = ο = ο (9Η2) β

(CH2) -N = c = 0 0 Continued pages (When the description page of the invention is not enough, please note and use the continued page) 10 200305582 玖, Description of the invention

Vn / CH2) 6 ~ or — (CH2) rN \) = 〇 (CH2) rN—c— (〇CH2CH2) j〇-CC- ο 〇 ((〇Η2) ΓΝγΝ-(CH2) 6- 〇I · 本The compounds of the invention of the formula 丨 can, for example, be made by the presence of a catalyst in which a diol (by which the compound of the formula R1 = 0H! Is obtained) or a functionalized 0H_Y_Ri (A) and phenylglyoxylic acid Esters (B) (for example, the corresponding methyl esters) are reacted to produce: 〇- 0 0 • I II cco-ch3 + HO-Y-Rt catalyst-► Δ vacuum 0- (B) (A) 0 0 M M CC-0-YR, 0) where 'Ri is as defined above. As a catalyst system, for example, a catalyst for transesterification reaction, which is familiar to those skilled in the art, such as dibutyltin oxide or p-toluenesulfonic acid, can be used. Some catalysts, although suitable for completing the reaction, cause the product to become discolored or rusty or difficult to remove from the reaction mixture. Suitable catalysts include sodium acetate, potassium acetate, magnesium acetate, barium acetate, zinc acetate, cadmium acetate, copper (II) acetate, cobalt (II) acetate, aluminum acetate, 15 calcium oxide, lithium methoxide, sodium methoxide, tetraisopropanol Titanium, aluminum triisopropoxide, lithium tert-butoxide, 4 · (difluorenylamino) pyridine and dibutyl diacetate (= Fascat 4200) [ Water content has nothing to do]. 0 Continued pages (Please note and use continuation pages when the invention description page is not enough.) 11 200305582 发明, invention description It is especially suitable for various kinds of salt, such as isopropyl alcohol clock, lithium acetate, lithium carbonate. Lithium acetate and calcium oxide are preferred. Lithium acetate is particularly suitable as a catalyst for the preparation of a compound of formula I in which R1 = 0H. The catalyst content is, for example, 0.1 to 20 mole% (based on 5 parts (B) of the glyoxylate group), but even a larger content can be used without adversely affecting the reaction process. Preferably, 4 mole% of the catalyst is used.

Advantageously, an excess of alcohol (A) is added and the methanol formed during the reaction is distilled off by applying a reduced pressure (about 5 to 300 Torr). This reaction can be carried out under normal pressure or vacuum, and the particular alcohol formed is distilled off in each case 10. The appropriate pressure is from 0.001 mbar to 1000 mbar, preferably from 5 to 10 mbar. The diethylene glycol content used may be, for example, 1 equivalent to 100 equivalents, which is based on phenylglyoxylic acid methyl ester (1 equivalent); preferably, 10 equivalents are used. The temperature of this reaction may be 20 ° c to 180 ° c. The reaction is preferably completed at 40 to 120 ° C (particularly 50 to 60 ° C). For example, any ester lower than 15 can be used as the glyoxylic acid component (B) (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or second butyl ester, etc.) . The reaction time is generally 2 to 80 hours, preferably 10 to 20 hours. As a solvent for the transesterification reaction, for example, an aromatic solvent such as benzene, toluene, cumene, o-, m-, or p-xylene or an isomeric mixture thereof, but it can also be used as a solvent. Ethers, such as diethyl ether, diisopropyl ether, butyl methyl ether, third butyl fluorenyl ether, 1,4-dioxane, tetrahydrofuran, etc., may also have a boiling point above 70 ° C hydrocarbon. Preferably, the reaction is completed without adding a solvent. Working up is done, for example, by washing the reaction mixture with water (removing the catalyst and unreacted diethylene glycol); drying is done by, for example, continuation of the next page (when the invention description page is insufficient, Please note and use the continuation sheet) 12 200305582 发明, description of the invention, such as adding a solvent (for example, toluene) that forms an azeotropic mixture with water and completing it by azeotropic distillation. Any diethylene glycol diester formed in the reaction is obtained by using isomers from benzene, toluene, cumene, o-, m-, or p-xylene or the like and / or diethyl ether, diisopropyl Ether, butyl methyl ether, tertiary butyl hydrazyl ether, 1,4-dioxane and other suitable organic solvents for extraction and removal. Furthermore, completion can also be accomplished by, for example, column chromatography (removal of desired by-products). The preferred eluent mixture for elution is ethyl acetate / hexane or other hydrocarbons (heptane, petroleum ether, etc.). The ratio of ethyl acetate to hydrocarbon may be 90:10 to 30:70, and preferably 50:50. II. A further possible method for obtaining the compounds of the invention comprises a base-catalyzed reaction of a phenylglyoxylate halide (C) (preferably a phenylglyoxylate gaseous) with an alcohol (A). ^^-CC-CI + HO-Y-ft, CC-0-YR, (C) ⑴ ⑴ 15 The bases used in these reactions are familiar to those skilled in the art. Aqueous alkali is not used. Examples of suitable bases include carbonates, tertiary amine bases, such as triethylamine, and pyridine. . IIb. A further possible method for obtaining the compounds of the invention comprises the catalytic reaction of phenylglyoxylic acid (S) with an alcohol and the addition of dicyclohexylcarbodiimide (DCC). (Please note and use the continuation sheet when you are using it) 13 200305582 Rose, invention description DCC S chemical agent '

00 CC-OH + HO — YR, ㈧ (S) III. Furthermore, the compound of the present invention can, for example, react the alcohol (A) with the corresponding phenylacetate (D) in the presence of a catalyst and Obtained by subsequent oxidation reaction: 〇 OS- C-〇GH3 + HO-Y-Ri Ή2 catalyst YR, (D) (A) 5 ό

0 1 OMC OMC can be used as a catalyst system, for example, as described in i. The oxidation step may be, for example, CTzem · C7 ^ m · C ^ mm (7 outer cedar, 3 completed with or synthesized and applied " PPW, P / 5. IV. Considered as the chemical formula for manufacturing the present invention A further method of the compound of I is, for example, the reaction of the corresponding hydroxy-substituted phenyl acetate (E) with the alcohol (A) and the subsequent oxidation reaction:

ΟΗ Ο • C —S-ο-CH3 + OH-Y-RJ OH 〇Y_Ri (E) (A) [〇] 0 Continued pages (If the description page of the invention is insufficient, please note and use the continued pages) 14 15 200305582 玖, description of the invention

0 0 II II C-C ~ 〇 ~ Y-R1 (1) 〇 5 Immunization reaction can be, for example, according to J. Chem. Soc. Chem. Comm. (1994), 1807 method i 氚. V. A further possible method for the production of the compound of formula i according to the invention The acid-catalyzed reaction comprising phenylcarboxylic acid cyanide (F) and alcohol (A):

+ ho-y-Rj h2o ^

Or 0 0 II II CC-〇-Y-R1 (F) (A) (I) 〇 VI · The compound of the formula I of the present invention is also possible, for example, by the presence of phenyl and dimeric compounds in the presence of aluminum chloride The Friedel-Crafts reaction of the oxycarboxylic acid gaseous compound (H) was obtained as follows: 0 0 0 Μ μ Al ^, _ Ο Ο + ci — ccoyr, AIC 丨 3, / Π \. Η " 1 ^ ^^-cc-0-γ- ^ (Η) (I). 15 Usable catalysts are familiar to those skilled in the art of the Friedel-Crafts reaction, such as gaseous tin, zinc gaseous, aluminum chloride, emulsified titanium, or acid earth . Reactions I, lib, III, and IV can generally be performed without using a solvent by using a reactant (a liquid, such as an alcohol) as a solvent. However, these reactions can also be completed in an inert solvent. Appropriate solvents include, for example, (note if the description sheet is not enough, please note and use the continuation sheet) 15 200305582 玖, description of aliphatic and aromatic hydrocarbons such as alkane and alkane mixture, cyclohexane, benzene , Toluene and xylene. Of course, the boiling point of these solvents is desirably higher than the alcohol formed during the reaction. Other remaining syntheses as listed above are advantageously performed in an inert solvent 5; for example, solvents as exemplified above are suitable.

It is advantageous to ensure that alcohols formed during the reaction are removed from the reaction mixture during the reactions I, III and IV. This can be done, for example, by the distillation described in I, and if appropriate, by applying a vacuum. The reaction is completed at various temperatures depending on the solvent and starting materials used. The temperatures and other reaction conditions required for the reaction in question are generally known and familiar to those skilled in the art. The reaction product can be isolated and purified according to a generally used method (for example, by crystallization, distillation, extraction, or chromatography).

The manufacture of the starting materials 15 required to synthesize the compounds of formula I of the present invention is generally known and familiar to those skilled in the art. Certain derivatives of the starting materials (B), (C), (D), and (F) are even, for example, commercially available. For example, phenylglyoxylate (B) is obtained from phenyl and appropriate oxygen. The Friedel-Krafts reaction of methyl carboxylic acid methyl chloride is obtained by esterification of phenylglyoxylic acid 20 chloride (C) with an alcohol. The phenylglyoxylic acid gaseous substance (C) can be obtained, for example, by a gasification reaction of an appropriate acid (for example, as SOC12). Phenylcarboxylic acid cyanide (F) can be obtained, for example, by reacting an appropriate acid chloride with CuCN. For example, phenylacetic acid methyl ester (D) can be produced by an acid-catalyzed reaction of phenyl-CH2-CN and methanol. This reaction is described on page 0 (continued when the description page of the invention is insufficient, please note and use the continued page) 16 200305582 发明, description of the invention, for example, CW / · 篇 / lag, 270. The corresponding phenyl-CH2-cyanide can be obtained from, for example, the corresponding gaseous substance and obtained using NaCN, for example, Org. Syn. Coll. Book I, 107 and Org. Syn · Coll. Book IV, 576 reveal. The synthesis of phenyl ethyl acetate is described, for example, in 5 Chem · Soc · Chem · Com (1969), 515. In this method, the phenyl bromide in the complex is in the presence of lithium / diethyl ether. Reacts with N2CH2COOC2H5. Another method (reaction of phenyl bromide with ethyl acetate and NaH) is described in, for example, J. Am. Chem. Soc. (1959) Red, 1627. J. Org. Chem. (1968) 21, 1675 describes the reaction of phenyl bromide with BrCH2COOC2H5 Grignard to form phenylethyl acetate (D). The production of alcohol (A) is familiar to those skilled in the art and is widely described in the literature. Many of these compounds are commercially available. Compounds of formula I having a hydroxyl group in the center are of particular interest. These compounds can also be used as starting materials for the manufacture of compounds of formula I, which are otherwise functionalized in the heart. Therefore, the present invention also relates to a method for manufacturing a compound of formula I (wherein, K is OH) as defined above, which is performed by using a phenylglyoxylic acid monoester of the formula Ο 0 0 -C-0 -R (II) wherein 20 R is a CrC4 alkyl group, especially methyl or ethyl, which reacts with a glycol of formula III HO-Y-OH (III), wherein Y is as defined above, 0 continued on the following page (invention When the instruction sheet is not enough, please note and use the continuation sheet) 17 200305582 玖, the description of the invention, as the catalyst system acetate, sodium acetate, potassium acetate, acetate, barium acetate, zinc acetate, cadmium acetate, copper acetate ), Cobalt (II) acetate, aluminum acetate, calcium oxide, lithium methoxide, sodium methoxide, titanium tetraisopropoxide, aluminum triisopropoxide, lithium third butoxide, 4- (dimethylamino) pyridine or di Dibutyltin acetate. 5 Further details regarding the reaction conditions are as shown in I above. The lover is a method in which lithium acetate is used as a catalyst, and also a method in which the reaction is completed at a temperature of 20 ° C to 180 ° C. Preferably, the amount of the catalyst is 0.1 to 20 mol% (based on the glyoxylate of the chemical formula (II) as a reference) 〇10 The compound of the chemical formula I whose center is OH is a light initiator which can be incorporated by itself However, it can also be used in the manufacture of other photoinitiators. Incorporable photoinitiators according to the present invention derived from compounds of Chemical Formula 1 (wherein K is OH, hereinafter referred to as Chemical Formula la), for example, urethanes derived from isocyanates and compounds of Chemical Formula la ; Carbamate derived from carbamate 15 base gas and compound of chemical formula la; Thio aminocyanate derived from thioisocyanate and compound of chemical formula la; from acid, acid gas, acid ester Acid anhydrides or phthalic anhydrides and acid esters derived from compounds of the chemical formula la; carbonates derived from chloroarsinates and compounds of the chemical formula la; glycidyl ethers and glycerol diethers derived from epichlorohydrins and compounds of the chemical la . When the compound of the chemical formula la is used in an amount less than the stoichiometric amount, the multivalent reaction partner of the compound of the chemical formula la produces a product that still has free unreacted functionality that can be incorporated.

In this regard, C6H5- (C0HC0) -0-CH2-CH2-0-CH2-CH2- 0 is used in the preparation of compounds of formula I that are functionalized (not with OH) in R! When not enough, please note and use the continuation sheet) 18 200305582 发明, invention description OH as a starting material is a special hobby. The following are examples of compounds with chemical formulae used as intermediates in the preparation of other recombinable photoinitiators: 〇τΥ, γ, 〇 = C = N—RrN = C = 〇

ο

Cl ·

Cl ο η σ ο ιι C,

ΟΥ ,,

α

Among them, RS, R9 and Υ are as defined above Q 10

Therefore, the present invention also relates to the use of compounds of formula I (whose center is OH) as photoinitiators for manufacturing incorporation (wherein & is SH, NR3R-(CO) -OH,-(c〇)- nh2, so3h, -c (r5) = cr6r7, 4, 〇- (c〇) -nh-r8-nco ^ -〇- (c〇) -r9. (c〇) .x; x R3j R4 > R5j

r7, r8, r9a X are the starting materials as defined above). 15 The present invention is also related to a method for manufacturing an incorporable photoinitiator of Chemical Formula I, in which the compound of Chemical Formula K with its central system OH) and isofluoric acid, carbamate gaseous compounds, and thioisopropyl Cyanate, acid gas, acid ester, acid anhydride, gas formate or epigasic alcohol is reacted. As a light-initiated reaction for starting green and nano-compounds from a compound of the formula I in which R1 is 0H, the materials and materials suitable are diisodiacetate and oligomeric isocyanate S, for example, containing hexadecanoate Methyl diisopropionate vinegar second page (turning page is not enough, please note the female continuation page) 19 ^ 20 200305582 2, 'diisocyanate, fluorenylmethyl-m-phenylene diisocyanate, 2,4-diisocyanato-i_methyl_cyclohexane, 1,3-bisisocyanatomethylbenzene, M-xylene diisocyanate, — diisocyanatomethyl-cyclohexane, isophorone diisocyanate, 5-isocyanate 5-acid-1-isocyanatomethyl-1,1,3- Trimethylcyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate, diphenyl methane 4,4, _ diisocyanate, 4,4'- Diphenylmethane diisocyanate, bis (4-isocyanatophenyl) methane, 4,4-oxybis (phenylisocyanate), 4,4, _diisocyanato-3,3'_di Methyldiphenylmethane, bis (4-isocyanato-3-methylbenzene10yl) formaldehyde , Dicyclohexylmethane 4,4, diisocyanate, ι, 3,5-tris (6-isocyanatohexyl)-[1,3,5] trihexyl-2,4,6-trione, 1 , 3,5-tris (6-isocyanatohexyl) biuret, N, N ,, 2-tris (6-isocyanatohexyl) iminodiamine diamidine, 1,3-bis (6-Isocyanatohexyl) _ [1,2] Diazetidin-2,4-dione, 2,5-2,6-ExoΛbisisocyanatofluorenyl_norbornane It 15 technical mixture of diisocyanato_2,2,4-trimethylhexane. The corresponding commercial product is sold under the name "Desmodur" by Bayer AG. If the compound of formula I modified with isocyanate is used in the photocurable composition as described above, it is also advantageous to use corresponding An isocyanate resin is used as the curable component. In this way, the compatibility of the photoinitiator with the formulation 20 to be cured is increased. The compound according to the formula 'Chemical Formula I may be used as an ethylenically unsaturated compound or contain this A photoinitiator for the photopolymerization of a mixture of compounds. Its use can also be mixed with different photoinitiators and / or other additives. Therefore, the present invention also relates to a photopolymerizable composition, which contains 0 continued The next page (if the invention description page is insufficient, please note and use the continuation page) 20 200305582 玖, invention description (a) at least one ethylenically unsaturated photopolymerizable compound, and (b) at least as a photoinitiator A compound of formula I, for this composition, in addition to component (b), it may also contain other photoinitiators 5 (c) and / or other additives (d). Unsaturated compounds may contain one or more Hydrocarbon double bond. It can be low molecular (monomer) or higher molecular weight (oligomer). Examples of monomers having a double bond are acrylates and methacrylates of alkyl and hydroxyalkyl groups, for example, Acrylic esters of fluorenyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl, isobornyl acrylate 10 and methacrylic esters of methyl and ethyl. Lovers also use silicon or fluorine to change Quality resins, such as silicone acrylates. Further examples include acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl esters (such as vinyl acetate), Vinyl ethers (such as isobutyl vinyl ether), styrene, alkyl- and halo-styrene, N-15 vinylpyrrolidone, vinylidene, and vinylidene. Monomers with several double bonds Examples are ethylene glycol diacrylate, propadiene diacrylate, neopentyl glycol diacrylate, hexamethylidene glycol diacrylate, and bisphenol A diacrylate, 4,4'-bis (2 -Propenyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, Pentaerythritol 20 triacrylate and pentaerythritol tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, and tris ( 2-propenylethyl) isocyanurate. Examples of higher molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated or containing vinyl-ether or epoxy groups Zhiju 0 Continued pages (If the description page of the invention is insufficient, please note and use the continued page) 21 200305582 玖, Description of the invention

Esters, polyurethanes and polyethers. Further examples of unsaturated oligomers are unsaturated polyester resins, which are generally made from maleic acid, phthalic acid, and one or more glycols, and have a molecular weight of about 500 to 3,000. In addition, vinyl ether monomers and oligomers can also be used, as well as maleate-terminated caps with polyester, polyurethane, polyether, polyvinyl ether, and epoxide backbones. Of oligomers. Combinations of oligomers and polymers carrying vinyl ether groups (as described in WO 90/01512) are particularly suitable, but copolymers of monomers functionalized with maleic acid and vinyl ether are also considered. Suitable unsaturated oligomers are also referred to as prepolymers. 10 Particularly suitable for, for example, ethylenically unsaturated carboxylic acids and polyols or polycyclic rings

Esters of oxides, and polymers having ethylenically unsaturated groups in the chain or in the pendant groups, such as unsaturated polyesters, polyamides and polyurethanes and their copolymers, alkyd resins, Polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, 15 polymers and copolymers having (meth) propylene groups in side chains, and one or more of these And other polymer mixtures. Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic and methacrylic are preferred. Suitable polyhydric alcohols are aromatic, and especially aliphatic and cycloaliphatic 20-valent alcohols. Examples of the aromatic polyol are hydroquinone, 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) -propane, Novolac resin, and resole resin. Examples of polyepoxides are those polyols (particularly aromatic polyols and epichlorohydrin). It is also suitable as a polyol containing polymers and copolymers containing hydroxyl groups in the polymer chain or side groups, for example, polyvinyl alcohol and its copolymers. Continued page (Insufficient invention pages, please note and use Continued) 22 200305582 玖, invention description or polyhydroxyalkyl methacrylate or its copolymer. A further suitable polyol is a polyester having a hydroxyl end group. Examples of aliphatic and cycloaliphatic polyhydric alcohols include alkylene glycols having preferably 2 to 12 carbon atoms, such as ethylene glycol, 2-, 2-, or propylene glycol, H,丨, 3 · or 込 4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, preferably 200 Polyethylene glycol up to 1500 molecular weight, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexyl glycol, 1,4-dimethymethylcyclohexane Burner, glycerol, tris (stone-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, 10 pentaerythritol, dipentaerythritol and sorbitol. Polyols can be partially or completely esterified with one or different unsaturated carboxylic acids, and free hydroxyl groups in the partial esters can be modified, for example, etherified, or esterified with other carboxylic acids. Examples of esters are: 15 dimethyl alcohol propylene tripropylene ester, trimethyl alcohol ethane tripropylene ester, dimethyl alcohol propylene trimethyl ester, trimethyl alcohol acetonitrile Trimethyl acrylate, tetramethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, tetramethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, di20 pentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol difluorenyl acrylate, Pentaerythritol trimethylpropionate g purpose, dipentaerythritol dimethyl propionate, dipentaerythritol tetramethyl acrylate, tripentaerythritol octamethyl propylene 0 renewal Page) 200305582 发明, description of the invention, sour vinegar, pentaerythritol diitaconic acid, dipentaerythritol triitaconic acid vinegar, dipentaerythritol pentaconic acid vinegar, dipentaerythritol hexaitaconate , Ethylene glycol dipropylene acid vinegar, u-butanediol diacrylic acid vinegar, butanediol dimethylacrylic acid vinegar, M · butanediol diitaconate, sorbitol tripropylene Folic acid 5 vinegar, sorbitol tetrapropionate vinegar, pentaerythritol modified tripropylene vinegar, sorbitol tetramethacrylic acid vinegar, sorbitol pentapropionic acid vinegar, sorbitol hexaacrylate, oligosaccharides Polyester acrylates and methacrylates, glycerol diacrylate and triacrylate, M-cyclohexane diacrylate, bisacrylates and bismethacrylates of polyethylene glycol with a molecular weight of 200 to 1500 10, or a mixture thereof. Also suitable as component (a) are the same or different unsaturated carboxylic acids and aromatic, cycloaliphatic and aliphatic 1 amines preferably having 2 to 6 (especially 2 to 4) amino groups The stuffed amine. Examples of these polyamines are ethylenediamine, 1,2- or 1,3-propanediamine, 1,2-, 1,3- or 1,4-butanediamine, 1,5-pentanediamine, hexane Diamine 15, octanediamine, dodecanediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bis-phenylenediamine, di-aminoethyl ether , Diethylene triamine, triethylene tetramine, bis (dot-aminoethoxy), or bis (amine-aminopropyloxy) ethane. Further suitable polyamines are polymers and copolymers having additional amine groups in the side chain, and oligomeric amines having amine end groups. Examples of these unsaturated fluorene 20 amines are: fluorenyl bispropenylamine, 1,6-hexamethylene bispropenylamine, diethylene triamine trimethacrylamide, bis (methacryl) Fluorenylaminopropoxy) ethane, dot-fluorenylpropenylaminoethyl methacrylate, and N [(cold-hydroxyethoxy) ethyl] propenylamine. Appropriate unsaturated polyesters and polyamides are derived from, for example, maleic acid and 0 continuation pages (if the description page of the invention is insufficient, please note and use the continuation page) 200305582 玖, invention description diol or diamine . Maleic acid can be partially replaced by other dicarboxylic acids. It can be used with ethylene unsaturated comonomers (for example, styrene). Polyesters and polyamines can also be derived from dicarboxylic acids and ethylene unsaturated diols or diamines, especially from longer chains having, for example, 6 to 20 carbon atoms. Examples of the polyaminophosphonate 5 are those composed of a saturated diisocyanate and an unsaturated diol or an unsaturated diisocyanate and a saturated diol. Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers include, for example, alkenyl groups such as ' ethylene, propylene, butene, and hexene, (meth) acrylates, acrylic fluorene, vinylene, and vinyl chloride. Polymers having a (meth) acrylate group in the side chain 10 are also known. Examples are the reaction products of epoxy resins based on Novolak resin with (meth) acrylic acid; homopolymers or copolymers of vinyl alcohol or its hydroxyalkyl derivative esterified with (meth) acrylate And homopolymers and copolymers of (meth) acrylates which have been esterified with hydroxyalkyl (meth) acrylates. 15 Suitable components (a) also include C which has been modified with primary or secondary amines

Esterates are described, for example, in US 3 844 916, EP 280 222, US 5 482 649 or US 5 734 002. These amine-modified acrylates are also referred to as amine acrylates. The amino acrylate can be, for example, UCB Chemicals 'trade names rtmEBECRYL 80, rtmEBECRYL 81, RTMEBECRYL 20 83, rtmEBECRYL 7100, BASF's trade name RTMLaromer PO 83F, RTMLaromer PO 84F, RTMLaromer PO 94F, Cognis' trade name rtmPHOTOMER 4775 F, rtmPHOTOMER 4967 F or Cray Valley under the trade names RTMCN501, RTMCN503, RTMCN550. 0 Continued pages (Please note and use continuation pages when the invention description page is not enough.) 25 200305582 发明, invention description The photopolymerizable compound can also be used by itself or in any desired mixture. Preferably, a mixture of polyol (meth) acrylates is used. 0 Binders can also be added to the composition according to the invention, which is particularly advantageous when the photopolymerizable compound is a liquid or viscous substance. The amount of the binder may be, for example, 5 to 95% by weight, preferably 10 to 90% by weight, and particularly 40 to 90% by weight, based on the total solid weight. The choice of adhesive is based on the field of use and its required properties, such as developability in aqueous and organic solvent systems, adhesion to substrates, and sensitivity to oxygen. Suitable binders are, for example, polymers having a molecular weight of about 50,000 to 20,000 (preferably 10,000 to 10,000). Examples are: homopolymers and copolymers of acrylic acid and methacrylate, such as copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (alkyl methacrylate 15), Poly (alkyl acrylates); cellulose esters and ethers such as cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl Methylal, cyclized rubber, polyethers, such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran; polystyrene, polycarbonate carbonate, polyurethane g, gasified polyhydrocarbons, Polyethylene terephthalate, polyethene 20 / vinylidene chloride copolymer, vinylidene copolymer with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copolymerization (ethylene / vinyl acetate) . Polymers such as polycaprolactam and poly (hexamethylene adipamide), polymers such as poly (ethylene glycol terephthalate) and poly (hexamethylene glycol succinate) Thing. 0 Continued pages (note that the invention description page is insufficient, please note and use the continuation page) 26 200305582 玖, description of the invention Unsaturated compounds can also be mixed with non-photopolymerizable film-forming components. These can be, for example, physically dried polymers or their solutions in organic solvents, such as nitrocellulose or cellulose acetobutyl, but they can also be chemically or thermally curable resins, such as , Polyisocyanate, poly 5 epoxide or melamine resin. The concomitant use of thermally curable resins is important for use in so-called hybrid systems, which are photopolymerized in the first step and crosslinked by thermal post-treatment in the second step. The light initiators according to the invention are also suitable as initiators for curing systems, such as oxidative drying, such as Lehrbuch der Lacke und 10 Beschichtungen Vol. III, 296-328, Verlag WA Colomb in der Heenemann GmbH, The compounds according to the invention described in Berlin-Oberschwandorf (1976) (for example, compounds of formula I whose center is OH) are also particularly suitable as photoinitiators for hybrid adhesive systems. These systems generally include at least one heat-curing component and one photochemical-curing component. The heat curing component is generally a two-component or multi-component reactive resin, preferably a polyol / polyisocyanate. Taking into account the photochemical curing component are all monomers, oligomeric or polymeric unsaturated compounds and mixtures customary for this purpose. The polymerization or crosslinking reaction is assisted by high-energy radiation and assisted by a photoinitiator. Instead. These compounds are described in detail above. Appropriate Example 20 also contains isocyanates of the "Desmodur series" as described above. A thermo / photochemical hybrid system can be obtained by mixing all the components together. The isocyanate component is advantageously added shortly before use. In order to avoid the premature complete curing of the thermally polymerized components, as is commonly used in the formation of polyurethane reaction resins. In order to completely cure the coatings prepared by such hybrid systems, apply 0 to the next page (invention When the instruction sheet is not enough, please note and use the continuation sheet) 27 200305582 玖 、 Introduction of the invention The covering is first irradiated in the manner conventionally used for radiation-curable systems, during which the rapid surface drying of the layer and the initial curing are achieved The final curing state is achieved when the thermal reaction (which can also be accelerated by heating) is completed. However, the curing effect can also be completed first by heating and then by ultraviolet rays. It is mainly based on purely drunk 5 thermally reactive resins. Compared to slow drying systems, the advantages of these systems are considerable time and energy savings; they also allow coated objects to be stacked immediately or processed further faster. The advantage of using the photoinitiator according to the present invention in the hybrid adhesive system is different from that of the traditional photoinitiator. In the final fully cured poly-10 compound material, no photoinitiator residue is detected. Or its photodecomposition product. Therefore, the polymer product exhibits greater final hardness; less adverse effects (such as odor or yellowing) caused by the initiator are less. Due to the OH group, according to the present invention The covalent incorporation of the photoinitiator into the polymer material is generated by the same amount of isocyanate 15 as the heat curing component in the hybrid binder system. Therefore, the present invention also relates to the above The composition described above, in addition to the photochemical curing component and component (b) and, if appropriate, (c) and (in addition to the sentence, also includes a heat-curable component. Where R! Is the chemical formula I of OH The compounds can be co-preceded by esterification with carboxylic acid-containing components in fully radiation-curable 20 systems and hybrid systems. Examples of such components include, for example, Phthalic acid, pyromellitic acid and its anhydride, and their equivalents since then It is derived from polymers and still contains at least one carboxylic acid functionality of its agglomerates or polymers. The photopolymerizable mixture may contain various additives in addition to the photoinitiator. Continued pages (Please note and use the continuation sheet) 28 200305582 玖, description of invention (d). Examples are thermal inhibitors, which are used to avoid premature polymerization reactions, such as hydroquinone, hydroquinone derivatives, p- 曱Oxyphenol, pip-naphthol or sterically hindered, such as' 2,6-di (third butyl > -p-cresol. To increase dark storage stability, for example, copper compounds such as copper Naphthenate, stearate or octanoate), fluorene compounds (for example, triphenylphosphine, tributylphosphine, diethylphosphite, triphenylphosphite, or triphenylphosphonium) Phosphate), quaternary ammonium compounds (for example, tetramethylammonium vapor or trimethylphenylphosphonium ammonium chloride) or hydroxylamine derivatives (for example, diethylhydroxylamine). In order to exclude atmospheric oxygen during the polymerization reaction, stone ballast or a similar wax-like substance can be added. Its 10 series is insoluble in the polymer. It migrates to the surface at the beginning of the polymerization reaction and forms a transparent surface layer to prevent air from entering. Equivalent may be applied in layers that are impermeable to oxygen. As the light stabilizer, an ultraviolet absorber may be added, for example, those having a hydroxyphenylbenzotriazole, a hydroxyphenylbenzoxazole, a oxalate or a hydroxyphenyl_s_trifluorene type. These compounds can be used by themselves or in a mixture (with or without hindered amines (HALS)). The following are examples of these ultraviolet absorbers and light stabilizers. · Phenylphenyl) -benzotriazole, for example, 2- (2, -hydroxy-5, -methylphenyl) benzotriazole, (3,5, -Di-Third-butyl-2, _hydroxyphenyl) benzotriazole, 2- (5'-Third-butyl-2, -hydroxyphenyl) benzotriazole, 2_ (2, hydroxy_5, _20 (m3-tetramethylbutyl) phenyl) benzotrisal, 2_ (3,, 5, _di_th ^: Butyl-2'-hydroxyphenyl)- 5-chlorobenzotriazole, 2- (3, -third butyl_2, hydroxymethyl, · methylphenyl), 5-chlorobenzotriazole, 2- (3, -second butyl_ 5, _third butyl_2, _hydroxyphenyl) benzotriazole, 2- (2, -hydroxy · 4, _octyloxyphenyl) benzotriazole, 2- (3 ', 5' -Di-tertiary pentyl-2'-hydroxyphenyl) benzotriazole, 2_ (3 ,, 5, _ _ second page (if the description page of the invention is insufficient, please note and use the continuation page) 29/200305582发明 Description of the invention Bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, third butyl-2, -hydroxy-5,-(2-octyloxycarbonyl Ethyl) phenyl benzotriazine, 2_ (3'_third butyl-5 '-[2- (2- Hexyloxy) _carbonylethyl] _2, pennylphenyl) -5-chlorobenzotriazole, 2- (3, -third butyl_2, _hydroxy-5,-(2-methyl5 Oxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2 (3, · third butyl-2, mesityl-5 '-(2-fluorenyloxyethyl) phenyl) -Benzotrisigma, 2- (3, -tertiary butyl · 2-transyl-5-(2-octyloxyepiethyl) phenyl) -benzotrisine, 2- (3, _ Third butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] _2, _hydroxybenzyl) _benzotriazole, 2- (3'-dodecyl- 2, -hydroxy-5, -methylphenyl) -benzotriazole and 2- (3'-third butyl-2, -hydroxy-5,-(2-isooctyloxycarbonylethyl) Mixture of phenylbenzotriazoles, 2,2, -methyl-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl · phenol ]; 2- [3, -Third-butyl-5,-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl] • benzotriazole and polyethylene glycol 300 Esterification product; [R-CH2CH2-COO (CH2) 3] 2-wherein R = 3, -third butyl-4,-15-methyl-5'-2H-benzotriazol-2-yl-benzene I. 2-Cyclophenylbenzene, such as 4-Cycloyl, 4-methoxy , 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2,4, -trihydroxy and 2'-hydroxy-4,4'-di Derivatives of methoxy. Cool of unsubstituted or substituted stupid formamidines such as 4-tert-butyl-20 phenylsalicylate, phenylsalicylate, octylphenylsalicylate Acid ester, diphenylfluorenyl resorcinol, bis (4-third butylbenzylhydrazine) resorcinol, benzophenacyl resorcinol, 3,5 · di-tert-butylbenzene_ 4-Hydroxybenzoic acid 2,4-di-second butyl acetoacetate, di · third butyl-4-acrylic acid hexadecyl vinegar, 3,5-di-third butyl-4-hydroxy Octadecyl Phenyl Acetate and 3,5_Di-0th Continued Page (Insufficient Use of the Invention Page, Please Note and Use Continued Page) 30 200305582 玖, Description of the Invention 2-methyl-4,6-di-tert-butylphenyl formate. L acrylic J1, such as cyano-dot, ethyl or isooctyl ester of 10,000-diphenylacrylic acid, α-methoxy-carbonyl cinnamate, "_cyano_stone-methyl- Phenyl or butyl ester of p-methoxy cinnamic acid, α-methoxy 5 carboxy-p-methoxy cinnamic acid methyl ester, and N-(/ 3-methoxy_carbonyl-methyl-cyanide Phenyl vinyl) -2 · fluorenyl · archyl. Fully hindered amine-, for example, bis (2,2,6,6 · tetramethylpiperidinyl) sebacate, bis (2,2, 6,6-tetramethylpiperidinyl) succinate, bis ..., ^ pentamethylpiperidinyl) sebacate, n-butyl_3,5_di_tertiarybutyl_4 • Hydroxybenzyl_ 10 malonate bis (1,2,2,6,6_pentamethylpiperidinyl) ester, 1_hydroxyethyl_2,2,6,6 · tetramethyl-4- Condensation product of hydroxyπ bottom bit and acetic acid, N, N, · bis (2,2,6,6 · tetramethyl-4-piperidinyl) hexamethylene diamine and 4.third octyl Condensation product of amino, 2,6-digas-l, 3,5-s-triazine, tris (2,2,6,6_tetramethyl_4_piperidinyl) nitrogen diacetate , Tetrakis (2,2,6,6-tetramethyl) -4-piperidinyl) -i, 2,3,4-butane 15 Tetrakis, I, 1-(L2-ethenyldiyl) -double 3,3,5,5-tetramethyl-pyrrolidone), 4-benzylidene-2,2,6,6 · tetramethylpiperidine, 4-stearyloxy_2,2,6, 6-tetramethyl brigade, bis (1,2,2,6,6-pentamethyl briquette) -2-n-butyl_2- (2-meryl, 3,5-mono-second Butyl benzyl) malonate, 3_n-octyl_7,7,9,9_tetramethyl-1,3,8_triazaspiro [4,5] decane_2, 4-dione, bis (1-octyloxy_ 20 2,2,6,6-tetramethylpiperidinyl) sebacate, bis (1-octyloxy_2,2,6,6- Tetramethylpiperidinyl) succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) hexamethylene diamine and 4-morpholino-2 Condensation product of 1,6-digas-1,3,5-triazine, 2 • chloro · 4,6-bis (4-n-butylamino group_2,2,6,6_tetramethylpiperidinyl group ) _1,3,5-Three hex condensation products with 1,2-bis (3-aminopropylamino) ethane, 2-Ga- | 3 Continued pages (Insufficient invention pages, please Note and use continued page) 31 200305582 582, Description of the invention 4,6-Difluorene n-butylamino-1,2,2,6,6-pentamethylpiperidinyl) -i, 3,5-triazine Condensation product with 1,2-bis (3-aminopropylamino) ethane, 8-acetamido_3_dodecyl-7,7,9,9_ Tetramethyl_1,3,8_triazaspiro [4.5] decane-2,4 · -SH 3-undecyl-1- (2,2,6,6-tetramethyl-4- Misaki Hiroshi-5 2,5-a-, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-Luyodo) Burning 2,5_di_, 2,4-bis [N- (l-cyclohexyloxy-2,2,6,6 · tetramethylpiperidin-4-yl) -N-butylamino] _6_ (2_Ethylethyl) amino_ι, 3,5_trifluorene, 2,4-bis [N- (l-cyclohexyloxy-2,2,6,6-tetramethylpiperidine- Condensation product of 4-yl) butylamino] -6-gas-s-triazine and N, N, -bis (3-aminopropyl) ethylenediamine. 10 6. Diacetate of oxalic acid, for example, 4,4'-dioctyloxy-oxadibenzidine, 2,2, -diethoxy-oxadibenzidine, 2,2, -dioctyloxy- 5,5, -Di-tertiary-butyl oxafenacetin, 2,2, -bis (dodecyloxy) -5,5, -Di-tertiary-butyl oxafenacetin, 2-ethoxyl -2'-ethyl-oxadibenzidine, ν, N, -bis (3-dimethylaminopropyl) oxadiamine, 2-ethoxy-5-tert-butyl-2,- Ethylamphetamine 15 amine and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tertiary butyloxantrol and o- and p-methoxy- Mixtures with o- and p-ethoxy-disubstituted stilbenes. 7 · 2- (2-Cyclophenyl) -1,3,5-trisodium, such as 2,4,6-tris (2-Cyclo-4-octyloxyphenyl-1,3,5 -Triazine, 2- (2-hydroxy-4-octyloxyphenyl) _4,6_bis20 (2,4-dimethylphenyl) -1,3,5-triad, 2 · (2 , 4-Diacrylphenyl) _4,6-bis (2,4-difluorenylphenyl) -1,3,5-trihexyl, 2,4-bis (2-hydroxy-4-propoxy) -Benzyl) · 6 · (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-meryl · 4 · octyloxyphenyl) · 4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy · 4 · dodecyloxyphenyl) -4,6-bis (2,4-dimethylbenzene Base) -1, 3, 5-three voices, 2_ [2- Jingji · 4_ 0 Continued pages (when the invention description page is insufficient, please note and use the continuation page) 32 200305582 玖 、 Invention description (2- 经Methyl-3-butoxy_propoxy) phenyl] _4,6_bis (2,4-dimethylphenyl) _1,3,5_triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) triazine and 2_ [4-dodecyloxy / twelve Carbooxy- (2-Ethylpropyl) oxy_2-Ethyl-phenyl] -4,6-bis (2,4-diamidino-5phenyl) -1,3,5-triazine. Phosphites and phosphites, Such as triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilaurylphosphite, tris (octadecane) Base) phosphite, distearyl, pentaerythritol diphosphite, tri- (2,4-di-third-butylphenyl) phosphite 10 acid salt, diisodecyl pentaerythritol diphosphite, bis -(2,4-Di-tert-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-tert-butylmethylphenyl) pentaerythritol diphosphite, bis-isodecyloxy- Pentaerythritol diphosphite, bis (2,4-di-third-butyl-6-methylphenyl) pentaerythritol diphosphite, bis- (2,4,6-tri-tert-butylphenyl) -Pentaerythritol diphosphite, tri 15 stearyl sorbitol triphosphite, tetra (2,4-di-tert-butylphenyl) -4,4'-bisphenylphenyl diphosphite, Isooctyloxy_2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-: ° dioxaphosphocine, 6- Fluoro-2,4,8,10-tetra-tert-butyl-12-fluorenyl-dibenzo [d, g] -1,3,2-dioxocyclic ring, bis (2,4-di- First Butyl-6-fluorenylphenyl) methylphosphite and 20 bis (2,4-di-third-butyl-6 · methylphenyl) ethylphosphite. Suitable as component (d Further examples of ultraviolet absorbers and light stabilizers are "Krypto-UVA", for example as described in EP 180 548. Latent ultraviolet absorbers can also be used, for example, as described by Hida et al. In RadTech Asia 97, 1997, on page 212. 0 Continued pages (Please note and use continuation pages when the invention description page is not enough.) 33 200305582 发明. Description of the invention In addition, additives commonly used in this technology (such as antistatic agents, flow modifiers and adhesion promoters) can be used. used.

A large amount of amine can be used as a further additive (d) to accelerate the photopolymerization reaction, for example, triethanolamine, N-methyl-diethanolamine, ethyl p-dimethylaminobenzoate or Michler ketone. The effect of amines can be promoted by the addition of, for example, aromatic ketones of the benzophenone type. Amines which are suitable as oxygen replenishers are, for example, substituted N, N-dialkylanilines as described in EP 339 841. Further accelerators, co-initiators and auto-oxidants are thiols, thioethers, disulfides and phosphines, for example as described in EP 438 123 and GB 2 180 358. It may also be added to the composition according to the present invention as a chain extender customary in this technique. Examples include thiols, amines, and benzothiazoles. Furthermore, the photopolymerization reaction can be accelerated by adding a photosensitizer (which shifts or broadens the spectrum sensitivity) as a further additive (d). These include, in particular, aromatic carbonyl compounds such as benzophenone derivatives, thioxanthone derivatives (also particularly isopropylthioxanthone), 15 anthraquinone derivatives, and 3-fluorenylcoumarin derivatives. , Bitriphenyl, styryl ketone and 3- (arylamidino) -thiazoline, camphorquinone and eosin, rhodamine and erythrosine sodium salt dyes. As photosensitizers, for example, the amines described above can also be considered. Further examples of these photosensitizers are 20 1. thioxanthone 11 ket 11 ketone, 2-isopropyl fluorenone, 3-isopropyl 17 ketone, 2-chloroxanthone, 2_12 Alkyl thioxanthone, 1-Ga-4-propoxy thioxanthone, 2,4-diethyl thioxanthone, 2,4-dimethyl thioxanthone, 1-methoxycarbonyl thioxanthone , 2-ethoxycarbonylthioxanthone, 3- (2-methoxyethoxycarbonyl) -thioxanthone, 0 Continued pages (If the description page of the invention is insufficient, please note and use the continued page) 34 200305582 发明, Description of the invention 'butoxycarbonylthioxanthone, Hongbutoxycarbonyl-7-methylthioxanthone, cyanothioxanthone, 1-ethoxycarbonyl-3-oxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone_, 丨 _ethoxycarbonyl_3-aminothioxanthone, 丨 _ethoxyrocarbylbenzylthiothioxanthone, 3, 4-di- [2- (2-methoxyethoxy) eth5oxycarbonyl] _thioxanthine_, 1 · ethoxycarbonyl-3- (1-methyl-1-morpholinylethyl > thioxanthone, 2-fluorenyl-6-dimethoxymethyl-thioxanthone, 2-methyl-6- (l, l-monomethoxybenzyl) · xanthone, 2 -Morinylmethylthioxanthone, 2 · methyl-6_morpholinomethylthioxanthine 'N-allyl thioxanthone-3,4-dicarboxyfluorenimine, N-octylxanthium __3,4-dicarboxyfluorenimine, tetramethylbutyl) _ 10 thioxanthone dicarboxylic acid Fluorenimine, 1-phenoxythioxanthone, 6-ethoxycarbonyl_2-methoxythioxanthone, 6_ethoxycarbonylmethylthioxanthone, thioxanthone_2_ polyethylene glycol Ester, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N_trimethyl-1-propane ammonium gas Compound. 2 · Benzenebenzene 15 Benzobenzene, 4-Phenylbenzenebenzene, 4-methoxybenzenebenzene, 4,4, -dimethoxybenzene, 4,4'-dimethylbenzene Benzene, 4,4, -Digas Benzenebenzene, 4,4, -Dimethylaminobenzene Benzene, 4,4, -DiethylaminoBenzene Benzene, Trimethylbenzene Methyl-4'-phenylbenzylbenzene, 2,4,6-trimethylbenzylbenzene, 2,4,6-trimethyl-4'-phenylbenzylbenzene, 4- (4_fluorenylthio) Phenyl) _Benzylbenzene, 3,3, di20methyl-4-methoxybenzylbenzene, fluorenyl_2_phenylbenzylbenzoate, 4 · (2_hydroxyethylthio) -Benzylbenzene, 4- (4-tolylthio) -phenylbenzylbenzene, 4-benzylidene-N, N, N-trimethylbenzyl ammonium vapor, 2-hydroxy_3- (benzene曱 醯 Basic oxygen group) -N, N, N-dimethyl-1 · Propyl chloride monohydrate, '(13-propenyl-1,4,7,10,13-pentaoxine Alkyl) _Benzylbenzene, 4-Benzamidine 0 Continued pages (When the description page of the invention is not enough, please note and use the continued page) 35 200305582 玖, Description of the invention fluorenyl N, N —fluorinyl also [2- (1-Atomyl 1-propylidene) oxy] ethyl-benzyl ammonium vapor; 3. 3-Pyridylcoumarin 3-Benzylpyridine Dentin, 3_benzylidene ·? _Methoxycoumarin, Hong 5 benzyl group_5,7-di (propoxy) coumarin, 3-benzyl group-M-di Chlorocoumarin, 3-benzopyrene + air coumarin, 3,3, -quinyl-bis [5,7_bis (propoxy) -coumarin], 3,3, quinylbis (7 · methoxycoumarin), 3,3, several bis (7-diethylamino-coumarin), 3_isobutyridinylcoumarin, benzamidine-5,7 -Dimethoxycoumarin, styryl-5,7 · diethoxycoumarin 10, 3_benzylidene_5,7-dibutoxycoumarin, 3.benzyl Fluorenyl-5,7_bis (methoxyethoxy) -coumarin, 3-benzylidene-5,7_bis (allyloxy) coumarin, 3-benzylidene- 7-Dimethylaminocoumarin, Dibenzidine_, Diethylaminocoumarin, 3-Isobutylamino_7_dimethylaminocoumarin, 5,7-Dimethoxy 3--3- (1-naphthylfluorenyl) -coumarin, 5,7-diethoxy-3 · (1-naphthylfluorenyl) -15 coumarin, benzamylbenzo [f] fragrant Coumarin, 7-diethylamino-3-coumaridinocoumarin, 3- (4-cyanobenzyl) _5,7_dimethoxyoxycoumarin; 4 · 3- ( Arylaminomethyl Methyl-2-benzylidenemethyl-naphthothiazoline, hydroxymethylbenzylidenemethyl-benzothiazoline, 3-ethyl-2-propylidenemethyl-naphthalene-20 thiazoline; 5. Other carbonyl compounds acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzophenone, 2-acetamidonaphthalene, 2-naphthalene, 9,10-anthracene, 9-fluorene Ketones, dibenzocycloheptanone, glutanone, 2,5-bis (4-diethylaminophenylidene) cyclopentanone, α_ (p-di-0 Continued pages (Instruction sheet is insufficient) (Please note and use the continuation sheet) 36 200305582 玖, description of the invention methylaminophenylidene) ketones, such as dimethylaminophenyl phenyl ketone, 3- (4-dimethylamino) Phenyl benzidine · 5 prepared propylene, 3-phenylthiophosphonate imine, N-methyl-3,5 · bis (ethylthio) -g tarimine. The curing method, especially for pigmented compositions (for example, pigmented with titanium dioxide), is assisted by the addition of components that form free radicals under thermal conditions as additional additives, for example, Aromatic compounds such as 2,2'-azobis (4-methoxy_2,4-di? Valeronitrile), triazene, diazosulfide, pentazene, or peroxy compounds, such as , Nitrogen peroxide or peroxycarbonate, for example, third butyl hydrogen peroxide, for example, as described in Ep 10 245639. The composition according to the present invention may contain a photoreducible dye as a further additive (G), such as, for example, glutathione, benzoxanthenium, benzothiaxanthin, thiazine, peronine, shikonine, or acridine dye , And / or dihalomethyl compounds which can be decomposed by radiation. Similar materials are described in, for example, Ep 445 624 15 〇 Further additional additives (d) (depending on the intended use) are fluorescent whitening agents, fillers, pigments (white and pigmented pigments), Colorants, antistatic agents, wetting agents or flow modifiers. The addition of glass microspheres or pulverized glass fibers (for example, as described in US 5 0137 68) is suitable for solidification of thick and colored coatings. The formulation may also contain colorants and / or white or pigmented colorants. Depending on the intended use, inorganic and organic colorants can be used. These additives are known to those skilled in the art; some examples are titanium dioxide pigments (for example, rutile or anatase type), carbon black, zinc oxide (such as zinc white), 0 Insufficient rewards are available, and the face has been sickened) 200305582 玖, description of the invention Iron oxide (such as iron oxide yellow, iron oxide red), chrome yellow, chrome green, nickel titanium yellow, ultramarine blue, cobalt blue, starvation , Recording yellow and cadmium red. Examples of organic colorants are mono- or bis-cobalt colorants and their metal complexes, phthalocyanine colorants, polycyclic colorants, such as perylene, anthraquinone, thioindigo, quinacridone, or tricyclic Phenylmethylpentane colorant and diketone-pyrrolo-pyrrole, isoindolinone, for example, tetragas isoindolinone, isoindolin, dioxazine, benzimidazolone, and quinophthalone material. The colorant can be used in the formulation itself or as a mixture. Depending on the intended purpose, the colorant is added to the formulation in an amount customary to this technique, for example, 0.1 to 60% by weight, 0.00 to 30% by weight, or 10 to 30% by weight ❶ / ❶ 10 Based on total mass. Formulations may also contain, for example, a very wide variety of organic colorants. Examples are azo dyes, hypofluorenyl dyes, anthraquinone dyes and metal complex dyes. Conventional concentrations are, for example, from 01 to 20%, especially from i to 5%, which are based on the total mass. 15 Depending on the formulation used, stabilizer compounds', especially amines, to neutralize acids can also be used. A suitable system is described in, for example, jp_Au_ 199610. Examples are pyridine and its derivatives. N-alkyl_ or N, N-dialkyl · aniline, sigmazine derivatives, sigma than 7 derivatives, and the like. The choice of additives depends on the field of use being explored and the nature of the field 20 desired. The above-mentioned additive (d) is customary in the art, and therefore is used in the amount customary in the art. The proportion of additional additives in the formulation according to the invention is, for example, 0.01 to 10% by weight, for example, 0.05 to 5% by weight / 0, especially 0.1 to 5% by weight. The present invention also relates to containing at least one dissolved or milk as component (a). 0 Continued pages

A composition of an ethylenically unsaturated photopolymerizable compound which is chemically dispersed or dispersed in water. Radiation-curable aqueous prepolymer dispersions are commercially available and are understood to be dispersions composed of water as a continuous phase and at least one prepolymer dispersed therein. The radiation-curable prepolymer or prepolymer mixture 5 is dispersed in water at a concentration of 20 to 95% by weight (particularly 30 to 70% by weight). In these compositions, the sum of the percentages stated for water and the prepolymer or prepolymer mixture is 100 in each case, auxiliaries and additives (eg, emulsifiers) (which are used in varying amounts depending on the intended use) Existence) is another. Radiation-curable aqueous prepolymer dispersions are known polymer systems comprising mono- or poly-functional ethylene having an average molecular weight Mη (g / mole) of at least 400 (particularly 500 to 100,000). Unsaturated prepolymer. However, prepolymers with higher molecular weights are also suitable, depending on the intended use. Use, for example, a polymerizable CC double bond-containing polyester having a maximum acid number of 10, a polymerizable CC double bond-containing polyether, a polyepoxide containing at least two epoxy 15 groups per molecule, and at least one Hydroxyl-containing reaction products of α, / 3-ethylene unsaturated carboxylic acids, polyurethane (meth) acrylates, and propylene copolymers containing α, / 5-ethylene unsaturated acrylic groups, such as EP 12 339 As described. Mixtures of these prepolymers can also be used. Also suitable is the polymerizable prepolymer described in EP 33 896, which is a thioether adduct having an average molecular weight of 20 Mn (g / mol) of at least 600, which likewise contains a polymerizable C-C double bond. Further suitable aqueous polymer dispersions based on special (fluorenyl) alkyl acrylate polymerization products are described in EP 41 125. Radiation-curable aqueous prepolymer dispersions may also contain additional additives (d) as described above as further additives, for example, dispersing aids, milk. (Use continuation sheet) 39 200305582 玖, invention description agent, antioxidant, light stabilizer, colorant, colorant, filler, for example, talc, gypsum, rutile, carbon black, oxidation, iron oxide, Reaction accelerators, flow agents, slip agents, wetting agents, thickeners, matting agents, defoaming agents and other adjuvants commonly used in surface coating technology. Appropriate dispersing agents include water-soluble high molecular weight organic compounds having polar groups, such as polyethylene glycol, polyvinyl alcohol, and cellulose. The emulsifiers that can be used are nonionic and, where appropriate, ionic emulsifiers. The photoinitiator of Chemical Formula I according to the present invention can also be dispersed in an aqueous solution 'and added to the mixture to be cured in a dispersed form. When blended with a suitable non-ionic, or (if appropriate) ionic emulsifier, the compound of formula I according to the present invention can be incorporated into water by mixing and 'e.g. grinding. Appropriate emulsions are obtained which can be used as photoinitiators, especially for aqueous photocurable mixtures as described above. In some cases it may be advantageous to use two or more photoinitiators according to the invention. Of course, it is also possible to use a mixture with a known photoinitiator. Examples are mixtures of camphorquinone, benzophenone, benzophenone derivative, acetophenone, acetophenone derivative, for example, α-Hydroxycycloalkylphenyl_ or 2-acyl-2-fluorenyl-1-phenylacetone, dioxooxyacetophenone, α-acyloxy or amine-acetophenone, for example, ( 4-fluorenylthiobenzylfluorenyl) -fluorene_fluorenyl 20-yl-1-morpholinoethane, (4-morpholinobenzyl) -1-phenylfluorenyl-1-dimethylamine Propane, 4-arylfluorenyl-1,3-dioxane, benzoin alkyl ethers and benzoin ketals, such as benzophenone dimethyl ketals, further phenylglyoxylates, and Derivatives, dimer phenylglyoxylates, diethylfluorenyl peresters, for example, benzopyrene tetracarboxylic acid peresters described in EP 126541, monofluorenyl phosphine oxidation Please note and use the continuation sheet when applying it.) 40 200305582 发明, invention description, for example, (2,4,6-trimethylbenzyl) phenylphosphine oxide, bisfluorenylphosphine oxide, bis (2,6-dimethoxyphenylfluorenyl)-(2,4,4-trimethylpent-1-yl) Oxide, bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide or bis (2,4,6-trimethylbenzyl) (2,4-dipentyl) Oxyphenyl) _phosphine oxide, 5 bisfluorenylphosphine oxide, halomethyltrisigmaine, for example, 2- [2 · (4-methoxyphenyl) -vinyl] -4,6- Bistrichloromethyl- [1,3,5] triazine, 2- (4-fluorenyloxy-phenyl) -4,6-bistrifluoromethyl- [1,3,5] triazine, 2 -(3,4-dimethoxyphenyl) · 4,6-bis-di-gas-methyl- [ι, 3,5] trihexyl, 2-methyl-4,6-bis-tri-gas-methyl · [ 1,3,5] Trihexyl, hexaarylbisimidazole / co-initiator system, for example, o-chlorohexaphenylbisimidazole in combination with 2-sulfo-10ylbenzothiazole; ferrocene cation compounds or Titanocene, for example, bis (cyclopentadienylbis (2,6-difluoropyrrolylbenzyl) titanium) titanium; or 0-fluorenyloxime ester compounds, for example, as described in GB 2 339 571. A borate compound can be used as a co-initiator. If the photo-initiator of the present invention is used in a hybrid system (in this context, it refers to a mixture of systems that can be cured with free radicals and cations), except in accordance with this Invention free radical curing agent Alternatively, cationic photoinitiators can be used, such as phenylperoxide (other suitable peroxides are described in US 4 950 581, line 19_17_25), aromatic fluorene-, scale- or iodonium salts , As described in us 4 950 581, line 18 to line 60 to line 19 to line 10, or cyclopentadienylarene iron (II) complex salt, for example, (77, cumene) (Π cyclopentadienyl) iron (II) hexafluoroscale salt or photo-latent acid based on prevention, such as GB 2 348644 US 4 450 598, US 4 136 055, WO 00/10972, WO 00 / 26219. The present invention also relates to an additional photoinitiator (c) of the chemical formula 0 continuation page (when the invention description page is insufficient, please note and use the continuation page) 41 (VIII), 200305582 发明, invention description VIII, Composition of compounds of IX, X, XI or / and XII:

(IX), 0 0 II II R34-Y-C ~ R35 R33 ^ 36 R39 ~ | '~ κ37 ^ 38 (X), (XI),

(XN), where R25 is hydrogen, Cj-Cis alkyl, Ci_C18 ^ oxy, -〇CH2CH2-OR29, morpholino, SCH3 or? \? 26 1 c-fluorene-r27 group ^ 28 Γ? H3 η system 2 to 10; each of G1 and G2 is an end group of a polymer unit, especially a gas or CH3; R26 is a hydroxyl group, CpCi6 alkoxy group, morphinyl, methionamine 15 or -0 (CH2CH20 ) m- (VC16 alkyl group; each of R27 and ruler 28 is hydrogen, CrC6 alkyl, benzyl, benzyl, 0 sequel (If the description page of the invention is insufficient, please note and use the continuation page) 42 200305582 玖, description of the invention Allyl, C6 Cl6 alkoxy or hepta (CH2CH20) m-CrC16 alkyl, or R27 and R28 form a cyclohexyl ring with the carbon atom bound thereto; m is 1 to 20 The number of R26, R27, and ρ and 28 are not CrCi6 alkoxy5 or -〇 (CH2CH2〇) nrCVCl6 alkyl; and Noch3 R29 is hydrogen, -C-ch :: CH2 or -C- c = ch2 · each of R30 and R32 is hydrogen or methyl;

Rn is nitrogen, methyl, 2-mercaptoethylthio or phenylthio, and the phenyl ring of phenylthio is unsubstituted or substituted with 4-, 2-, 2,4-, or 2,4, The 6-position is substituted with C! -10 C4 alkyl; R33 and each are individually Ci- (: 2G alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl, or biphenyl, these groups are Unsubstituted or halogenated,

CrCu alkyl or / and CrCi2 alkoxy substituted, or r33 is a 5- or 6-membered heterocyclic ring containing s • or N-

II 15 —. -R35 R35 is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenyl, these groups are unsubstituted or substituted with one or more halogen, c, c4 alkyl or / and CrC4 alkoxy Group substitution, or R35 is a 5- or 6-membered heterocyclic ring containing S- or N-;

Each of Rm and Rn is a cyclopentadienyl group, which is unsubstituted or substituted with 20 Ci-Cu alkyl, CrC18 alkoxy, cyclopentyl, cyclohexyl, or halogen mono-, di-, or tri- -Replacement; and each of anti-38 and R39 is a phenyl group, which is 0 in the ortho position of the titanium-carbon bond. Continued on the next page (if the description page is insufficient, please note and use the continued page) 43 200305582 (ii) At least one of the invention descriptions is substituted with a fluorine atom or cf3, and it may contain a pyrrolinyl or polyoxanyl group as a further substituent on the aromatic private ring, each of which is unsubstituted or substituted by Mono- or Ci-Ci2 alkyl, bis (CrCi2 alkyl) aminofluorenyl, morpholinomethyl, C2-C4 alkenyl, fluorenylmethyl, ethoxymethyl5, trifluorenylpentane Group, methylamino, fluorenyl or phenyl,

^ 40 or R38 and R39 are one \> one R41 or

> = N R42 R40, R41, and R42 are each hydrogen, halogen, C2-C12 alkenyl, CrCu alkoxy, c2_Ci2 alkyloxy interrupted by one to four oxygen atoms, cyclohexyloxy, cyclo Amyloxy, phenoxy, benzyloxy, phenyl or biphenyl radicals not substituted for 10 generations or substituted with CrC4 alkoxy-, halo-, phenylthio- or thiol- , Where r40 and r42 are not both hydrogen at the same time, and at R40

N

r41 group N at least one R4O or R42 group is a CrC12 alkoxy group, a C2-C12 alkoxy group interrupted by 15 of one to four oxygen atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or benzo Alkoxy; E! Is O, S or NR43; R43 is C 1 -C8, or basic or loxyl;

Yi series c3-c12 alkylene, butenyl, butynyl, or non-continuous-0 continuation page (when the description page of the invention is insufficient, please note and use the continuation page) 44 200305582 发明, description of the invention 0- or -NR44- intermittently one or more C4-C12 alkylene groups, or phenylene, cyclohexyl,

R44 is hydrogen, c, c4 alkyl or c2-c4 hydroxyalkyl. 5 Preferred composition is compound of formula VIII, IX, X, XI, and XII, wherein R25 is hydrogen, -0CH2CH2-OR29,? Fluoro, SCH3 or-? H31 G1--CH2 ~ C--G2; r26 is hydroxyl, crc16 alkoxy, morpholino or dimethylamino; each of 10 r27 and r28 is hydrogen, crc4 Alkyl, allyl, phenyl, benzyl or crc16 alkoxy, or R27 and R28 together with the carbon atom to which they are attached form a cyclohexyl ring;

II _C—CH = CH. R30, R31 and R32 are hydrogen; 15 R33 is CrC12 alkyl, unsubstituted phenyl or phenyl substituted with CrC12 alkyl or / and crc12 alkoxy; 〇_ 丨 丨 a R34 series-heart; and R35 is phenyl, which is substituted with one or more Crc4 alkyl or / and Crq alkoxy substituents. 0 Continued pages (Please note and use the continuation pages when the invention description page is insufficient.) 200305582 玖, the compounds with the best chemical formulas VIII, IX, X, XI, and XII are hydroxycyclohexylphenyl ketone and 2-hydroxy -2-methyl-1-phenylacetone, methyl phenylglyoxylate, phenyl- (C0) (C0) -0CH2CH20CH2CH20- (C0) (C0) -phenyl, (cardiomethylthiobenzene (Methylamino) -1-methylmorpholinoethane, (4-morpholinylbenzylbenzyl-1-dimethylaminopropylpropane, (3,4-dimethoxybenzene) (Methylamino) -1-benzyl-1-dimethylaminopropane, (4-morpholinobenzyl) -1- (4-methyl-benzyl) -1-dimethyl Amino propane, benzophenamine dimethyl ketal, (2,4,6-trimethylphenylphenylfluorenyl) phenylphosphine oxide, bis (2,6-dimethoxybenzyl) -(2,4,4-trimethylpent-1-yl) phosphine oxide, bis 10 (2,4,6-trimethylphenylfluorenyl) phenylphosphine oxide or bis (2,4, 6-trimethylbenzyl)-(2,4-di-phenyloxyphenyl) phosphine oxide and dicyclopentadienyl-bis (2,6-difluoro-3-pyrrolo) titanium Furthermore, the preferred composition is R27 in Chemical Formula VIII. Each of r28 is a C, C6 alkyl group or a cyclohexyl ring with a carbon atom bound to it, and R26 is a radical. Compounds with chemical formulas VIII, IX, X, XI and / or XI ( = Photoinitiator component (c)) The compound of the chemical formula in the mixed mixture (= photoinitiator component (b)) is 5 to 99%, for example, 20 to 80%, preferably 25 to 75% 〇20 A special enthusiast is a composition as described above, which contains a photoinitiator mixture of chemical formulas j VIII, IX, X, XI, and / or Xu, and is a liquid at room temperature. Chemical formulas VIII, IX The production of X, XI, and XII compounds is generally known to those skilled in the art, and some of these compounds are commercially available. Chemistry 0 Continued Page (Insufficient invention pages, please note and use continued Page) 46 200305582 (ii) Description of the invention The manufacture of oligomeric compounds of formula VIII is described in, for example, Ep 161 463. The manufacture of compounds of chemical formula IX can be found in, for example, Ep 209 831. The compounds of formula X Manufacturing systems are disclosed, for example, in EP 7 508, EP 184 095 and BG 2 259 704. Compounds of formula XI The system 5 is described in, for example, EP 318 894, EP 318 893 and EP 565 488. The production of compounds of chemical formula XII is described in, for example, us 6 048 660 〇 The photopolymerizable composition advantageously contains A photoinitiator at a content of 0.05 to 20% by weight (for example, 0.05 to 15% by weight, preferably 0% to 5% by weight based on a composition of 10). When the mixture is used, the photoinitiator content shown is related to the total content of all photoinitiators added, i.e., photoinitiator (b) and photoinitiator (b) + (c). The photopolymerizable composition can be used for various purposes, for example, as printing inks, for example, screen printing inks, rubber plate printing inks, or 15 offset printing inks, as transparent coatings, and as color coatings. As a white coating, for example, it is used for wood or metal, as a powder uncoated, as a coating for paper, wood, metal or plastic, etc., as a structure and as a sign for roadside curing by sunlight. Coatings for photocopying methods, for Wang Xi photography δ self-recording materials, for image recording methods or for the manufacture of printing plates that can be developed using organic 20 solvents or aqueous alkaline media, for the production of screen printing Cover, dental filling compound, as an adhesive, as a pressure sensitive product, as a laminated resin, as a photoresist, for example, electroformed photoresist, etching photoresist or durable photoresist , Liquid and dry film form, as a photo-structured dielectric, and as a solder mask for electronic circuits (continued on the next page), the description of the invention, as Color filters for any type of display screen or photoresist that forms structures during the manufacture of plasma displays and electrochromic displays, used for the manufacture of optical switches, light barriers (interference barriers), and solidified (transparent molds) UV curing) or three-dimensional objects according to stereolithography methods (for example, described in US 4 575 5 330), composite materials (for example, styrene polyester, which may include glass fibers and / or other fibers and other additives Agents) and other thick-layer compositions that coat or seal electronic components or as coatings for optical fibers. Furthermore, the composition is suitable for making optical lenses, such as contact lenses or Fresnel lenses, and for making medical devices, aids or implants. Furthermore, the 10-group composition is suitable for producing gels having thermal interconversion properties. These gel systems are described, for example, in DE 197 00 064 and EP 678 534. The composition may additionally be used in dry film coatings, for example, the Paint & Coatings Industry, April 1997 or Plastics World, Volume 54, Number 7, 48 (5 ) Page. 15 The compounds according to the present invention can also be used as initiators for emulsion polymerization, bead polymerization, or suspension polymerization, or as initiators for the polymerization of fixed-position liquid crystal monomers and oligomers, or as An initiator that fixes dyes to organic materials. For surface coatings, a 20% mixture of prepolymer and polyunsaturated monomer is generally used, which additionally contains a single unsaturated monomer. The prepolymer in this case specifically determines the properties of the surface coating film, and those skilled in the art can influence the properties of the cured film through its variations. The polyunsaturated monomer acts as a cross-linking agent, which renders the surface coating film insoluble. Monounsaturated monomers act as reactive diluents, whereby viscosity is reduced without the use of solvents. 0 Continued pages (Please note and use continuation pages when the invention description page is not enough.) 48 200305582 玖, invention description Unsaturated polyester resin is generally used together with a single unsaturated monomer (preferably styrene). Component system. For photoresist, a special one-component system is generally used, for example, polymaleimide, polyarylpropenearene or polyimide, as described in DE 2 308 830. 5 Furthermore, the compounds and mixtures thereof according to the present invention can be used as free radical photoinitiators or photoinitiator systems for radiation-curable powder coatings. The powder coating may be mainly a solid resin and a monomer containing a reactive double bond, for example, maleate, vinyl ether, acrylic ester, propylamine, and a mixture thereof. Free radical UV-curable powder coatings can be obtained by combining unsaturated 10 polyester resin with solid acrylamide (eg, methacrylamide aminoglycol methyl ester) and radical light according to the present invention. Starters are formulated by mixing, for example, the radiation curing of M. Wittig and Th. Gohmann's 1993 Conference Proceedings, Radtech Europe, "Powder Coatings," as described in the publication. Similarly, free radical UV curable The powder coating 15 can be configured by mixing an unsaturated polyester resin with a solid acrylate, methacrylate, or vinyl ester and a photoinitiator (or a photoinitiator mixture) according to the present invention. Powder The coatings may also contain binders, as described in DE 4 228 514 and EP 636 669. The UV-curable powder coatings may also contain white or colored pigments. For example, in particular, rutile / di 20 titanium oxide can be used at a concentration of up to about 50% by weight to obtain a cured powder coating with good hiding power. This treatment method generally involves spraying the powder with electrostatic or tribostatic methods On a substrate (for example, metal or wood), the powder is melted by heating, and after forming a smooth film, it is exposed to ultraviolet and / or visible light, for example, using a moderate pressure mercury lamp, a metal halide lamp, or 0 times. Pages (turning the pages without checking the dirt, the young chicks look at them) 49 200305582 发明, description of the invention Gas lamps make the coating radiation curing. The radiation-curable powder coating is superior to the corresponding heat-curable coating. The advantage is that the flow time after the powder particles have been melted can be extended as desired to ensure the formation of smooth and high-gloss coatings. Unlike thermal curable systems, radiation-curable powder coatings can also be formulated with 5 ' Melting at a lower temperature without the undesired effect of shortening its useful life. Therefore, it is also suitable as a coating for heat-sensitive substrates such as wood or plastic. In addition to containing a photoinitiator according to the present invention In addition, the powder coating formulation may also contain an ultraviolet absorber. Suitable examples are those previously listed in the above-mentioned points. The photocurable composition of the present invention is suitable, for example, as all kinds of substrates Of Cladding materials, such as wood, fabric, paper, ceramic, glass, plastic, such as polyester, polyethylene terephthalate, polyolefin, or cellulose acetate, especially in film form, and metals, such as, Ai, Cu, 15 Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO2, a protective layer or (for example, by imagewise exposure) an image can also be applied. The substrate can be applied by applying a liquid composition , Solution or suspension to the substrate for coating. The choice and concentration of the solvent are mainly dominated by the nature of the composition and by the coating method. The solvent must be inert, that is, it must not enter into the component 20 It is chemically reactive and needs to be able to be removed again when drying after the coating operation. Suitable solvents include, for example, ketones, ethers and esters such as f-ethyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexyl, N-methyl. Ratio of ketones, di-smoke, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, dimethoxy-2-propanol, 1,2-dimethoxyethyl , Ethyl acetate, n-butyl acetate, and 3- 0 continuation pages (if the invention description page is not enough, please note and use the continuation page) 50 200305582 玖, invention description ethyl ethoxypropionate. This formulation can be uniformly applied to a substrate by known coating methods, such as spin coating, dipping, doctor blade coating, curtain coating, painting, spraying (especially by electrostatic spraying), and reverse coating. Roll coating can also be performed by electrophoresis. This photosensitive layer can also be applied to a temporary flexible support 5 and then transferred to the final substrate (eg, a copper-plated circuit board) by transferring this layer through lamination. The coating (layer thickness) and the properties of the substrate (layer substrate) depend on the intended application. Those skilled in the art will understand the thickness of layers suitable for exploring applications such as photoresist, printing ink, or paint. The layer thickness range 10 generally includes a value of about 0.1 " 111 to more than 10 mm, which depends on the application field. The radiation-sensitive composition according to the present invention is also used, for example, as a negative photoresist, which has very high photosensitivity and can be developed without expansion in an aqueous alkaline medium. It is suitable as a photoresist for electronics (such as resistors, 15 etching resists), in liquid and dry films, as a solder resist, and as a color filter for any type of display screen. Resistors, or structures formed during the manufacture of plasma displays and electrochromic displays, in the manufacture of printing plates (for example, offset printing plates), in the manufacture of printing blocks for letterpress printing, for lithography, for gravure Printing, rotary printing on rubber plates 20 or screen printing blocks, making relief prints, for example, making braille, making molds, etching or molding, or as micro-resistors for making integrated circuits. This composition can also be used as a photo-structurable dielectric for coating materials or as an insulator coating for computer chips, printed circuits and other electrical or electronic components. Possible layer supports and 0-continued pages used to treat coated substrates (note that the pages are not covered, note and continue pages) 51 200305582 发明, description of the invention The conditions are changed accordingly. The compounds according to the invention can also be used to make single- or multi-layer materials for single- or multi-color image recording or image reproduction (photocopying, #imaging). These materials can also be used in test systems. In this technique, a formulation containing 5 microcapsules is used, and for image generation, the exposure step is followed by a heating step. These systems and technologies and their applications are described in, for example, ⑽ 5 376 459 〇 for photographic information recording, its use, such as #, polyboxes, cellulose acetate or plastic coated paper; for offset Printed blocks, such as special 10-treated aluminum, are used in the manufacture of printed circuits, such as copper-plated laminates, and are used to make integrated circuits on Shixi wafers. Typical layer thicknesses for photographic materials and offset printing blocks are generally about 0.5 / ^ 111 to 10 / Zm, and for printed circuits are 1.0 / im to 100ern. After the substrate has been coated, the solvent is generally recovered by drying to form a photoresist coating on the support. The term "imaging" exposure includes exposure using a mask with a predetermined pattern (eg, transparent), a laser that moves on the surface of a coated substrate (eg, under computer control) and produces an image in this manner Beam exposure and computer controlled electron beam irradiation. LCD masks can also be used, which can be controlled by pixel by pixel to generate digital images, for example, A Bert% h JY · Jezequel, JC · Andre in Journal of Photochemistry and Photobiology A ·· Chemistry 1997, 107, pages 275-281 and K.-P Nicolay in Offset Printing 1997, 6 pages 34-37. Conjugated polymers (for example, polyaniline) can be continued from half-zero pages by doping with protons (inventory description pages are not enough, please note and use continuation pages) 52 200305582 Conductive state. The photoinitiator according to the present invention can also be used for imagewise exposure of polymerizable compositions containing these polymers to form a conductive structure (in the illuminated area) that can be embedded in an insulating material (unexposed region). These materials can be used as, for example, 5 components or connection components for making electrical or electronic parts. After imagewise exposure of this material and before development, the thermal treatment can advantageously be performed for a relatively short time. During the heat treatment, only the exposed areas are thermally cured. The temperature used is generally 50 to 150 ° C, preferably 80 to 130 ° C; the heat treatment period is generally 0.25 to 10 minutes. 10 Photocurable compositions can also be used in methods for making printed blocks or photoresists, for example, DE 4 013 358. In this method, the composition is exposed to visible light at a wavelength of at least 400 nm before, at the same time as, or after the image-type irradiation. After exposure and selective heat treatment, the unexposed areas of the photosensitive coating are removed using a developer in a manner known per se 15. As already mentioned, the composition according to the invention can be developed in an aqueous alkaline medium. Suitable aqueous alkali developer solvents are especially aqueous solutions of tetraalkylammonium hydroxide or alkali metal silicates, phosphates, hydroxides or carbonates. If desired, in addition, a relatively small amount of a wetting agent and / or an organic solvent may be added to this solution. Typical 20 organic solvent systems that can be added to the developer fluid in small amounts, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone, and mixtures of these solvents. Light curing is important for printing inks because the drying time of the adhesive is a determining factor for the production rate of the image product and needs to be on the order of fractions of a second. Ultraviolet curable inks are especially important for screen printing, rotary printing of rubber plates, and 0-continued pages (if the description page of the invention is insufficient, please note and use the continued page) 53 200305582 发明, description of the invention Offset printing system is particularly important. As already mentioned, the mixture according to the invention is also very suitable for making printing plates. For this application, for example, soluble linear polyamides or styrene / butadiene or styrene / isoprene rubber, polyacrylates or polymethyl methacrylates with carboxyl groups, polyvinyl groups Mixtures of alcohols or urethane acrylates with photopolymerizable monomers, for example, propylene or methacrylamide or propylene or methacrylic esters and photoinitiators. Films and plates made from these systems (wet or dry) are exposed by the original negative (or positive), and the unexposed portions are subsequently eluted with a suitable solvent. Another application area for light curing is metal coatings, such as coatings to sheets and pipes, cans or bottle closures, and plastic coatings (such as PVC-based flooring or wall coverings). ) Light curing. Examples of photocuring of paper coatings include the application of a colorless top layer to a label, record sleeve or book cover. Fans also use the compounds of the present invention in the curing of molded articles made from composite materials. This composite is composed of a free-standing matrix material (for example, woven glass fibers, or in addition, plant fibers) [see H Mieck, T. Reussmann in Kunststoffe 85 (1995), 366-370], which is a light-curing formulation Objects immersed. Molded articles made from composite materials made using the compounds according to the invention are highly mechanically stable and resistant. The compounds according to the invention can also be used as photocuring agents for molding, impregnating and coating materials', for example as described in EP 7086. These materials are, for example, thin-layer resins (highly required for curing activity and yellowing resistance), and fiber-reinforced molding materials (for example, planar or longitudinal or transverse wave-shaped light plates). Methods of making these molding materials (such as manual lay-up method, fiber spraying, spinning or winding method) 0 Continued pages (Please note and use the continuation page when the description page of the invention is insufficient) 54 200305582 玖The description of the invention is described in "Glasfaservertarkte Kunststoffe" by P. Selden, Springer Verlag Berlin-Heidelberg-New York 1967, p. 610. Objects that can be manufactured according to this method are ship-shaped objects, cardboard or triple plywood Glass fiber reinforced plastic coating on both sides), pipes, sports equipment, roof coverings, containers, etc. Further examples of molding, impregnating and coating materials are glass fiber containing molding materials (GRP) Thin layers of UP resins, such as corrugated boards and paper laminates. Paper laminates can be based on urea or melamine resins. The thin layer is made on a support (eg, a film) before the laminate is manufactured. The photocurable composition according to the present invention can also be used for casting resin or for packaging of objects 10 (for example, electronic components, etc.). In addition, it can also be used for lining of holes and pipes. For curing, moderate Powerful mercury lamps can be used, such as those commonly used in UV curing, but lower intensity lamps, such as TL 40W / 03 or TL40W / 05, are also particularly hobby. The intensity of these lamps roughly corresponds to daylight Strength. Direct sunlight can also be used for curing. Further advantages 15 Series composite materials can be partially cured in the plastic state removed from the light source, and accept the forming effect, and then completely cured. The light initiator according to the present invention is also applicable. It is used as a composition for the coating of optical fiber. Generally, optical fiber is coated with a protective coating directly after its manufacture. The glass fiber is stretched, and one or more coatings are then coated 20 to glass fiber. Generally, one, two, or three coatings are applied, and the surface coating, for example, is colored ("ink layer or ink coating"). Furthermore, several The coated optical fibers can be put together in a bundle and coated together, that is, fiber cables. The composition according to the present invention is generally suitable for any of these coatings and needs to be exhibited over a wide temperature range Good softness, good 0 continued pages (hair When the instruction sheet is not enough, please note and use the continuation sheet) 55 200305582 玖 、 The tensile strength, toughness and fast UV curing characteristics of the invention are explained. Each coating material is mainly internal (generally a soft coating material) , Outer primary and secondary (generally coatings that are harder than inner coatings), tertiary or cable coatings, which can include at least one radiation-curable oligomer, at least one radiation-curable oligomer Monomer diluent, at least one photoinitiator, and additives. Generally, all radiation curable polymers are suitable. Preferably they have at least 500 (e.g., 500-10000, 700-10000, 1000-8000, or 1000 -7000), especially urethane oligomers, which contain at least one unsaturated group. Preferably, the radiation curable oligomer has two end-capped functional groups. The coating may contain not only a specific oligomer, but also a mixture of different polymers. The manufacture of suitable oligomers is known to those skilled in the art, for example, published in US 6,136,880, which is incorporated herein by reference. Polymerization system, for example, by combining an oligomeric diol (preferably a diol having 2 to 10 polyoxaalkylenes) with a diisocyanate or 15 polyisocyanate and a vinyl functional group. Saturated monomers (for example, by reaction with an alkyl (meth) acrylate). Specific examples of each of the above components and appropriate proportions of these components are shown in US 6,136,880, which is incorporated herein by reference. Radiation curable monomers can be used in a manner that controls the viscosity of the coating formulation 20. Therefore, a low-viscosity monomer having at least one functional group capable of photo-initiating polymerization is used. The content system is, for example, selected so that the viscosity is adjusted in the range of 1,000 to 10,000 mPa, that is, generally, for example, 10 to 90 or 10 to 80% by weight is used. The functional group of the monomer diluent is preferably of the same kind as that of the polymerizing component. For example, acetic acid or ethyl acetate scale functionality and higher calcining group. , Please note and use the continuation sheet) 200305582 玖, invention description or polyether part. Examples of monomeric diluents suitable for coating compositions for optical fibers are published in US 6,136,880, column 12, line 11 £, which is incorporated herein by reference. In the main coating, preferably, a monomer having an acrylate or vinyl ether function and a polyether moiety of 4 to 20 carbon atoms is used. Specific examples are those incorporated by reference and shown in the U.S. patents cited above. The composition may also include poly (siloxane) as described in US 5,595,820 to improve the formulation on optical fiber glass substrates. Adhesive properties. Coating composition 10 generally also contains further additives, such as antioxidants, light stabilizers, ultraviolet absorbers such as those listed above, especially RTMIRGANOX 1035, 1010, 1076, 1222, R ™ TINUVINP, 234 , 320, 326, 327, 328, 329, 213, 292, 144, 622LD (all provided by Ciba Specialty Chemicals), RTMANTIGENEP, 3C, FR, 15 GA-80, rtmSUMISORB TM.061 (by Sumitomo Chemical

Industries Co.), RTMSEESORB 102, 103, 501, 202, 712, 704 (supplied by Sypro Chemical Co "Ltd.), RTMSANOLLS770 (supplied by Sankyo Co. Ltd.) rtmIRGANOX 1035, 1010, 1076, 1222, RTMTINUVIN P , 234, 320, 326, 327, 328, 329, 213, 292, 20 144, 622LD (all provided by Ciba Specialty Chemicals), R ™ ANTIGENE P, 3C, FR5 GA-80, r ™ SUMISORB TM-061 ( (Supplied by Sumitomo Chemical Industries Co.), RTMSEESORB 102, 103, 501, 202, 712, 704 (by Sypro

(Provided by Chemical Co., Ltd.), RTMSANOLLS770 (continued by Sankyo Co. 0 (inventory description page is insufficient, please note and use the continuation page) 57 200305582 发明, description of the invention.

Ltd.) to avoid staining of the coating, especially during processing, and to improve the stabilizer of the cured coating. Special enthusiasts are stabilizer mixtures of sterically hindered piperidine derivatives (HALS) and sterically hindered compounds, such as IRGANOX 1035 and TINUVIN 292, for example, a 1: 1 mixture. Furthermore, the additives are, for example, moisturizing agents and other additives which are effective for the rheological properties of the coating. Furthermore, an amine (e.g., diethylamine) may be added. Other examples of additives as a component of the coating of optical fibers are silane coupling agents, for example, T-aminopropyltriethoxysilane, T-mercaptopropyltrimethoxysilane, r-fluorenylpropene Oxypropyl-trimethoxysilane 'SH6062' SH6030 (provided by Toray-Dow Corning Silicone Co., Ltd.), KBE 903, KBE 603, KBE 403 (provided by Shin-Etsu Chemical Co., Ltd.). In order to avoid coloration of the coating, this composition may also contain a fluorescent additive or an optical brightener, for example, rtmUVITEX OB (Ciba 15 Specialty Chemicals). The light according to the present application in the coating composition of optical fiber The initiator can be mixed with one or more other known photoinitiators. Especially mono- or bisfluorenylphosphine oxides, for example, diphenyl-2,4,6-trimethylbenzyl Phosphine oxide, bis (2,4,6-trifluorenylbenzyl) -phenylphosphine oxide 20 (®IRGACURE819), bis (2,6-dimethoxybenzyl) -2, 4,4-trimethylphenylphosphine oxide; α-hydroxy ketones, for example, 1-hydroxycyclohexylphenyl ketone (®IRGACURE 184), 2-hydroxy-2-methyl-1-phenyl-acetone ( ®DAROCUR 1173), 2-hydroxy-l- [4- (2-hydroxyethoxy) phenyl] -2-fluorenyl-1-acetone (®IRGACURE 2959); α-amino ketones, for example, 2- A0 Continued pages (If the description page of the invention is insufficient, please note and use the continuation page) 58 200305582 玖 、 Invention base-1-[4- (methylthio) phenyl] -2- (4-? Lynnyl) -1-propanone (⑧IRGACURE 907), 2-phenylfluorenyl-2- (dimethylamino) -1- [4- (4-? (Phenyl) phenyl] -1-butyl is the same as (®IRGACURE 369), 2- (4-methylphenylfluorenyl-2- (dimethylamino), small [4- (4-morpholinyl) benzyl Methyl] -1-butanone, 2-phenylfluorenyl-2- (difluorenylamino) small 5 [3,4-monomethoxyphenyl] -1-butanone; benzophenone, for example, benzene Toluene, 2,4,6-trimethylbenzene, 4-methylbenzene, 2-methylbenzene, 2-methoxycarbonylbenzene, 4,4'-bis (gas Fluorenyl) benzylbenzene, 4-chlorobenzylbenzene, 4-phenylbenzylbenzene, 4,4, bis (dimethylamino) benzylbenzene, 4,4, -bis (diethylamino) ) Benzenebenzene, methyl 2-benzylbenzoyl benzoate, 3,3, _dimethyl10methoxybenzophenone, 4- (4-methylphenylthio) benzene, 2,4,6-trimethyl-4'-phenyl-phenylhydrazine, 3-fluorenyl-4, -phenyl-phenylhydrazine and ketal compounds, such as' 2,2-dioxo- i, 2-diphenyl-ethanone (⑧IRgacURE 651); monomer or dimer phenylglyoxylate, such as methylphenylglyoxylate, 5,5-oxo-di (ethylene glycol) Oxydicarbonylphenyl) or n (benzylidenecarbonyl) ethane 15 alkane. Particularly suitable for use with mono- or bis-fluorenylphosphine oxide and / or α-hydroxy ketone The mixture is obviously 'to promote the properties of the photoinitiator, the formulation may also include sensitizers, such as amines. The coating is applied on, wet on dry, or, wet on wet " In the first case 20, after the first coating is applied, the curing step with ultraviolet irradiation is completed before the second coating is applied. In the second case, the two coatings are applied and cured together by ultraviolet irradiation. In this application, curing with ultraviolet radiation generally occurs in a nitrogen atmosphere. In general, all radiation sources commonly used in actinic technology can be used for light 0 continuation pages (turn over 1 [without inspection, face notes and dirty pages) 59 200305582 发明, invention description curing of fiber coatings . For example, as shown below. Generally, moderate pressure mercury lamps or / and Fusion D lamps are used. Furthermore, flash is also suitable. Obviously, the emission of the lamp corresponds to the absorption of the photoinitiator or photoinitiator mixture used. The optical fiber coating composition can also be cured by irradiation with an electron beam, especially with a low-power electron beam, for example, as disclosed in WO 98/41484. In order to distinguish the different fibers in the module, the fibers can be covered with a third colored coating ("ink coating"). The composition used for this coating, except for the polymerizable component and the photoinitiator ' Also contains colorants or dyes. Examples of colorants suitable for optical fiber coating are inorganic colorants such as titanium dioxide, oxide, zinc sulfide, barium sulfate, aluminum silicate, calcium silicate, carbon black, black Iron oxide, copper chromite black, iron oxide, chrome oxide green, iron blue, chrome green, purple (for example, manganese violet, phosphoric acid phosphate, CoLiP04), lead chromate, lead molybdate, titanate and flash Gravel-like beads and metal-like colorants, and organic colorants, such as monoazo colorants 15, an azo colorant, an azo concentrated colorant, yalconone colorant, di-sigmaine purple, hidden color Pigments, perylene pigments, thioindigo pigments, phthalocyanine pigments, and tetragas isoindolinones. Examples of suitable pigments are carbon black for black coatings, and one for white coating oxidation Titanium, diarylamine yellow or diazo-based colorants for yellow coatings, phthalocyanine blue for blue coatings, and others 2〇cyanine, anthraquinone red, naphthol red for red coatings, mono-azo-based colorants, quinacone colorants, anthraquinone and perylene, and for green coatings Phthalocyanine green and nitroso-based colorants, mono-atom and " a-atom-based colorants for orange coatings, σ-quina-based colorants, awakening and second leather inlay Benzene, quinacone violet, basic dyes for purple coatings, and sialos (continued on the pages of the invention description, please note and use the continuation sheet) 60/200305582 玖, Description of the invention. Colorants based on bad voices. Those skilled in the art know how to formulate and combine further colorants appropriately, even if more colored coatings are needed (such as water, brown, gray pink, etc.). Colorants The average particle size is generally about 1 # m or less. The size of commercial colorants can be reduced by grinding if necessary. Example 5 For example, 'colorants can be added to the formulation in the form of a dispersion to simplify the formulation. Mixing of other components. Colorants, for example, dispersed in low viscosity liquids (for example, reactive diluents) Organic pigments are preferably used. The appropriate content of the pigments in the ink coating is, for example, 1-20, 1-15, preferably 1-10% by weight. 10 Ink coatings generally also contain a lubricant to Provides improved break-out properties of single-coated optical fibers from the matrix. Examples of such lubricants are silicones, fluorinated oils or resins, etc., preferably lithone oils or functionalized dream compounds For example, a silicone diacrylate is used. The composition according to the present invention is further suitable as a substrate material for a coated 15-fibre component. That is, the number in the third coating which is distinguished by different colors. The main, second (and in some cases the third) coated fibers are combined in the matrix. The coating of the component is preferably a release agent in addition to the additives shown above for light installation. Individual fibers are easily accessible during fiber cables. Examples of these 20 release agents are Teflon, syringone, syrup, fluorocarbon oil or resin. The release agent is suitably used in an amount of 0.5 to 20% by weight. Examples of ink coatings and matrix materials for coated optical fibers are shown in U.S. Patent Nos. 6,197,422, 6,130,980 and EP 614 0099, which are incorporated herein by reference . 0 Continued pages (Please note and use continuation pages when the invention description page is not enough.) 200305582 玖, invention description The composition and compound according to the invention can also be used to manufacture optical waveguides and optical switches, using exposure and unexposed Refractive agent differences between regions arise. It is also important that the photocurable composition is used for image processing methods and light generation of information carriers. For this application, as described, the layer (wet or dry) applied to the support is a light mask and is irradiated with ultraviolet or visible light, and the unirradiated area of the layer is treated with a solvent (= Developer). The photocurable layer is also applied to the metal by an electrodeposition method. The exposed region is a polymer ' via the parent link and is therefore insoluble and remains on the support. When properly colored, visible images are formed. When the carrier is a metallized layer, after exposure and development, the metal can be etched away in the unexposed area and strengthened by electroforging. In this way, printed circuit boards and photoresists can be produced. The photosensitivity of the composition according to the present invention is generally extended from about 200 nm to about 600 nm (in the ultraviolet field). Appropriate radiation is, for example, light 15 or light from artificial light sources. Therefore, a large number of different kinds of light sources can be used. Point light sources and flat radiators (lamp arrays) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium-voltage, high-voltage, and low-pressure mercury arc radiators, if appropriate, doped metal halides (metallic compound lamps), microwave-excited metal vapor lamps, excimer lamps, Actinic fluorescent tube, fluorescent lamp, argon incandescent lamp 20, electronic flash, photo flood light, light emitting diode (LED), electron beam and X-ray. The distance between the lamp and the substrate to be exposed according to the present invention may vary depending on the type and intensity of the lamp to be used, and may be, for example, 2 cm to 150 cm. Particularly suitable for laser light sources, for example, excimer lasers, such as Krypton-F lasers, for example, exposure at 248 nm. Visible light 0 Continued pages (When the description page of the invention is not enough, please note and use the continued page) 62 200305582 玖. Lasers within the scope of the description can also be used. It can be used to produce printed circuits in the electronics industry, lithographic offset printing plates or relief printing plates, and photographic image recording materials using this method. Therefore, the present invention also relates to a photopolymerization method for a non-volatile monomer, oligomeric or polymerized compound containing at least one ethylenically unsaturated 5-double bond. The method includes irradiating light with a range of 200 to 600 nm as described above. The composition. The present invention also relates to the use of a compound of the formula: as a photoinitiator for photopolymerization of a non-volatile monomer, oligomerized or polymerized compound containing at least one ethylenically unsaturated double bond with light in the range of 200 to 600 nm. 0 The present invention also relates to the use of the above composition and a method for manufacturing colored and uncolored surface coatings and printing inks (for example, screen printing inks, offset printing inks, and rubber rotary printing inks) , Powder coating, printing plate, adhesive, dental composition, optical wave guide, optical switch, 15 color test system, composite material, glass fiber cable coating, screen printing engraving template, resistance Materials, color filters, packaging for electrical and electronic components, manufacturing magnetic recording materials, manufacturing three-dimensional objects by stereolithography, photocopying, and image recording, especially holographic alpha recording, Color materials, decoloring materials for image recording materials, a method of using micro 20 capsule image recording materials. The invention also relates to a coated substrate, which is coated on at least a surface with a composition as described above, and a method of photographically producing a relief image, wherein a coated substrate is coated with Image-wise exposure, then remove the unexposed part with solvent. This image-type exposure can use a mask or 12 continuation pages. Exposure using a laser beam is a particular hobby. Not only does the compound according to the invention have a photoinitiating effect, it can also be incorporated and tethered to the formulation to be polymerized by its special substituents, that is, it can be combined with any desired composition of these formulations. Component reaction, whether or not these component 5 participate in the photopolymerization reaction thereafter, and therefore, it is firmly bound to the formed polymer structure. The compound of formula I according to the present invention, whose center is OH, exhibits further important properties in addition to the properties described above, as it is an important intermediate in the manufacture of compounds of formula I that are further functionalized. 10 The following examples further illustrate the invention. In the rest of the description and patent application, parts and percentages are by weight unless otherwise indicated. For alkyl or alkoxy groups containing more than 3 carbon atoms, if the isomer form is not indicated, it should be understood in each case that it refers to the individual n-isomer. I: Embodiment 3 15 Example 1: 〇

II ac, / 0-ch2ch2-o-ch2ch2-oh a 137.9 g of phenyl glyoxylate, 891.7 g of diethylene glycol and 2.2 g of lithium acetate dihydrate at room temperature with the initial charge at 1.5 liters Inside a multi-necked flask equipped with a distillation device. With stirring, the reaction vessel was evacuated slowly to 8 to 10 mbar. The reaction mixture was then heated to 50 to 60 ° C. After about 72 hours, all the methanol that had been formed was removed by distillation and the reaction was complete. The reaction mixture was poured into a separating funnel together with 500 ml of water, and extracted three times with 100 ml of toluene, and then extracted with 500 ml of diethyl ether. Continued pages ) 64 200305582 发明 The invention description is taken five times. The ethereal phase was mixed, dried over sodium sulfate and filtered. The product was obtained after evaporation of the solvent (using a rotary evaporator). The structure and composition were confirmed by NMR spectroscopy and HPLC (high pressure liquid chromatography). N = C = 0 None-Example 2-Manufacturing-(〇. 啊 2) 2-〇-0 ^-. ^ {^] ^ 3 h4h3 ch3 5phenylglyoxylic acid 2- [2- (5-isocyanato-1,3,3-trimethylcyclohexylmethylcarbamoyloxy) -ethoxy] • Ethyl ester in argon, 4.28 g of 15 g of toluene in Example 1 of phenylglyoxylic acid (2-hydroxyethoxy) ethyl ester and 3.99 g of 5-isocyanato-1- Isocyanatomethyl-1,1,3-trimethylcyclohexane (isophorone diisocyanate 10, Fluka) was prepared in a 50 ml multi-necked flask with a starting charge and placed in a Reflow at 110 ° C. After 18 hours, the solution was cooled and the toluene system was concentrated using a rotary evaporator. The residue was dried under high vacuum for 2 hours. 8.2 grams of a thick yellow oil was obtained. The conversion and composition of the product were confirmed by ih_NMr spectrum and IR spectrum (NCO band spectrum). 15 Elemental analysis: C24H32N2〇7% C [Calculate / Discover]% H [Calculate / Discover]% N [Calculate / Discover] 62.59 / 63.55 7.00 / 7.07 6.08 / 6.07 〇〇〇_ Example 3: Manufacturing QfM monobenzyl Alginic acid 2- {2- [4- (4-isocyanatophenylhydrazone) _phenylaminocarbamyl 20-yloxy] -ethoxybutyrate under argon, 2 in 15 grams of toluene · 14 grams of 2-benzylglyoxylic acid (2-hydroxyethoxy) ethyl ester of Example 1 and 2.24 grams of 4,4, -diphenyl formaldehyde 0 Continued pages (If the description page of the invention is insufficient, please note and (Use continuation sheet) 65 200305582 发明, description of the invention Burned diisocyanate (Desmodur VL. Bayer) is placed in a 50 ml multi-necked flask with the initial charge and refluxed at 110 ° C. After 19 hours, the solution was cooled and the toluene system was concentrated using a rotary evaporator. The residue was dried under high vacuum for 2 hours. 4.6 grams of a thick, slightly brown oil was obtained. The conversion and composition of the product mixture were confirmed by iH-NMR spectrum and IR spectrum (NCO band spectrum). Elemental analysis: C27H24N207% C [Calculate / Discover]% H [Calculate / Discover]% N [Calculate / Discover] 66.39 / 67.54 4.95 / 5.19 5.73 / 5.52 W 9 / (ch2) 6-n-c- (〇ch2ch2) 2 ~ occ- and Example 4: Manufacturing o = c = ishch2 > 6-n) = 〇 \ 〇Η2) ΓηΝ _ ^ (〇〇η2〇Η2) γ〇χ ^ = C = | sHCH2) 6-N / (CH2 ) "N = C = 0 N > = 〇 (CH2) rH—C- (〇CH2CH2) 5-〇-CC-^^ Phenylacetic acid 2- (2- {6- [3- (6- Isocyanatohexyl) -2,4,6-trioxo-5- (6- {2- [2- (2-oxo-2-phenylacetamidooxy) · ethoxy] -ethoxy Ethylaminoamino group 15hexyl)-[1,3,5] triazin-1-yl] -hexylcarbamoylethylethoxy) ethyl ester and phenylglyoxylic acid 2- (2- { 6- [3,5-bis (6-isocyanatohexyl) -2,4,6-trioxo-1,3,5] triazinane-l-yl} • hexylcarbamoyloxy) _ Ethoxy) ethyl ester, 2.14 grams of benzene of Example 1 in 15 grams of toluene under argon, 20-glyoxylic acid (2-hydroxyethoxy) ethyl ester and 3.02 grams of 1,3,5-tri (6-Iso-0 continuation page (note that the invention description page is insufficient, please note and use the continuation page) 66 200305582 玖, invention description cyanatohexyl)-[1,3,5] trioxane-2,4 Butrione (Desmodur N 3300, Bayer) was placed in a 50 ml multi-necked flask with initial charge and refluxed at 110 C. After 16 hours, the solution was cooled and the toluene system was evaporated using a rotary evaporation method to ' Concentrated. The residue was dried for 3 hours under a vacuum in the south. 5.3 grams of a thick 5 thick colorless oil was obtained. The conversion and composition of the product mixture were confirmed by the NMR spectrum and IR spectrum (NCO band spectrum). As for the light The initiator, single product and double product are present in equal proportions. Elemental analysis · 〇481164 team 016 and C36H50N6〇n% c [calculate / discover]% H [calculate / discover]% N [calculate / discover] 10 58.53 / 58.42 6.67 / 6.71 9.75 / 9 18 Example 5: Manufacture 9 9 (Ch2CH2〇> 2IW- (CH beer-heart heart- (〒H2) 6 N = C = 〇 and (CH2) 6 N = C = 〇 1,3-bis (6- {2- [2- (2-oxo-2-phenylacetamidooxy) -ethoxy] -ethoxycarbonylamine 15-ylhexyl) -5- (6-iso Cyanatohexyl) biuret and 1- (6- {2- [2- (2-oxo-2-phenylethenyloxy) · ethoxy] -ethoxycarbonylamino} _hexyl > 2.14 grams of 3,5_bis (6-isocyanatohexyl) biuret in 15 grams of toluene under argon under Example 1 Glyoxylic acid (2-hydroxyethoxy) ethyl ester and 2.86 g of 1,3,5-tris (6-iso20 cyanatohexyl) biuret (Desmodur N 3200, Bayer) are given at the beginning. The contents were placed in a 50-liter multi-necked flask and refluxed at ii ° C. After 19 hours, the solution was cooled and the toluene series was concentrated using a rotary evaporator. Residues on the next page (if the description page of the invention is not enough, please note and use the continued page) 67 200305582 说明, description of the invention Dry under high vacuum. 4.8 grams of a thick, colorless oil was obtained. The conversion and composition of the product mixture were confirmed by 1H-NMR spectrum and IR spectrum (NC band). As for the photoinitiator, the single product and the dual product are present in equal proportions. 5 Elemental analysis: C47H66N6015 and C35H52N601 ()% C [Calculate / Discover]% H [Calculate / Discover]% N [Calculate / Discover] 58.91 / 59.22 7.11 / 7.14 10.05 / 9.67 0 0 1? Example 6:-(C ^ CHpj-CN-iCH ^ N7 ^ N- (CH2) rN = C = 0 0 phenylglyoxylic acid 2- (2- {6- [3- (6-isocyanatohexyl) -2,4-di Oxy- [1,3] 10 Diyadidine ° -1_yl] -hexylaminomethylmethyloxy} -ethoxy) ethyl ester 2.14 g of 15 g of toluene in argon Phenylglyoxylic acid (2-hydroxyethoxy) ethyl ester of Example 1 and 3.02 g of 1,3-bis (6-isocyanatohexyl)-[1-3] diamididine_2,4_ The diketone (Desmodur Ν3400, Bayer) was placed in a 50 ml multi-necked flask with the initial charge and refluxed at u0 ° C 15. After 19 hours, the solution was cooled and the toluene system was concentrated using a rotary evaporator. The residue Dry under high vacuum. 5.2 grams of a thick, colorless oil was obtained. The conversion and composition of the product mixture were confirmed by iH-NMR and IR spectra (NCO band spectrum). Elemental analysis: C28H38N409 20% C [Calculate / Discover ]% H [Calculate / Discover]% N [Calculate / Discover] 58.53 / 58.57 6.67 / 6.95 9.75 / 9.63 〇〇 〇 Example 7: Manufacturing- (ch2ch2o) factory g-c-ch2 0 Continued page (Review of the financial application, and the certificate depends on) 68 200305582 Rose, description of the invention phenylglyoxylic acid (2-epoxyethylene Alkylmethoxy-ethoxy) 〇; Lli manufactures diethylene glycol monoglycidyl ether H0- (CH2〇) d2— 26.53 grams of diethylene glycol and 0.25 grams of lanthanum perchlorate hexahydrate in a nitrogen atmosphere And 50 ml of toluene were initially injected into a 350 ml sulfonation flask equipped with a strengthened 5 condenser and a spiral stirrer, and heated to 105 ° C. After reaching the initial temperature of 105 ° C, the temperature was increased Maintaining fixation, 21.3 grams of epichlorohydrin was added dropwise over 70 minutes. After stirring at 105 ° C for 14 hours, 30 ml of toluene was added to the reaction mixture for the convenience of removing any remaining ones by azeotropic distillation thereafter. At normal pressure, about 30 ml of azeotrope was distilled off. After cooling to 48 to 50 ° C, about 19 g of diazobicycloundecene was dripped in over 30 minutes, and the mixture was After stirring for 2 hours, after cooling to room temperature, the lower phase of the two-phase reaction mixture was adjusted to Ph 5 to 8 with acetic acid, and Alkoxy each diluted and about 100 mL of brine and extracted three times. After dried over magnesium sulfate, the obtained crude product was concentrated to dryness to 15, and 27.1 g (73% of theory) of slightly yellow sticky oil resistance is obtained. Twelve grams of the crude product was purified by flash chromatography (800 grams of silica gel 60 F; ethyl acetate 95: methanol 5). The desired product is obtained in the form of a slightly yellowish oil of approximately 85% purity (determined by GC). According to the W-NMR spectrum, the by-products (15%, determined by GC) are the following compounds: Λ 20 H0- (CH2CH20) -c-ch2o-c-c-ch2 1H-NMR spectrum of diethylene glycol monoglycidyl ether (At CDC13, relative to trimethylsilane [TMS] as a standard, in ppm): 0 Continued pages (If the description page of the invention is insufficient, please note and use the continued page) 69 200305582 发明, Description of the invention

2 · 61-2 · 63 and 2.79-2.83 (2 m, Ha); 3.16-3 · 18 (m, Hb); 3.38, 3.44 and 3.81-3.86 (2 dxd, He); 3.60-3.75 (m , Hd, He, Hf,

Hg) i3NMR spectrum of 5 diethylene glycol monoglycidyl ether (in CDCI3, relative to TMS as a reference standard, in ppm): 44.2; 50.8; 616.6; 70 · 4 · 70.7; 72.0; 72.6: L2i Production of phenylglyoxylic acid (2-oxiranylmethoxy-ethoxy) 217 mg of phenylglyoxylic acid fluorenyl ester, 195 mg of diethylene glycol monoglycid obtained according to Example 10 7 · 1 Glyceryl ether and 10 mg of lithium acetate were placed in a pear-shaped flask with a starting shot. The flask was rotated in a rotary evaporator at a bath temperature of 60 ° C and a reduced pressure of 150 mbar. After 2 hours, the bath temperature was increased to 70 ° C. and the pressure was reduced to 100 mbar. After another 2 hours, the reaction solution was subjected to chromatography on silica gel using 1: 1 hexane · ethyl acetate. The title 15 compound was obtained as a slightly yellow oil. LH_NMR spectrum of benzyl glyoxylic acid (2-oxiranylmethoxy_ethoxy) (in CDC13, relative to TMS as a standard, in ppm):

0 0 Hf II 11 I I c-c-o-c—C-0—

2.58-2.60 and 2.76-2.79 (2 m, Ha); 3.14-3.16 (m? Hb); 3.38-

200305582 发明. Description of the invention i3c, MR spectrum of diethylene glycol monoglycidyl ether (in CDCi3, relative to TMS as a standard, in ppm) ... 44 2,5〇8,64 9,68 7, 70.6, 70.7, 72.0, 128.9, 130.1, 132.5, 135.0, 163.8, 186.2. Example 8 5 A photocurable formulation was prepared by mixing the following components: 89.0 parts of epoxy acrylate (80% in hexanediol diacrylate; Ebecryl® 604) 10.0 parts of polyethylene Diol 400 diacrylate (Sartomer @ SR 344) I. 0 parts of a flow modifier (Ebecryl (R) 35 ° > 10 2% of the compound of Example 1 was added to the formed formula. The formula was 6 / / m knife was applied to the sheet and irradiated with 2 medium pressure mercury lamps (80W / cm). The cured layer was obtained. Examples 9-14 The following formulations were made for Examples 9 to 14:

15-Component A II. 38 parts of hydroxyl-containing polyacrylate, 70% in butyl acetate (Desmophen A 870; Bayer AG) 21.23 parts of polyester polyol, 75% in butyl acetate (Desmophen VP LS 2089; Bayer AG) 20 0.55 parts of flow modifier (Byk 306; Byk Chemie) 32.03 parts of methanol-component B (using amount is shown in Table 1) Isocyanate-containing amino group Formate acrylate (Roskydal UA vp LS 2337, Bayer AG) 0 Continued page (If the description page of the invention is insufficient, please note and use the continued page) Concentrations shown in Table 1 were incorporated into component A and stirred. Component B is then added and distributed evenly. The prepared sample was applied to a glass plate with a 250 # m grooved knife. The solvent was then flashed off at room temperature. After flash evaporation, the UV spectrum was recorded (UV / 5 visible spectrometer Perkin Elmer Lambda 900). Then, the sheet was placed on a hot plate having a temperature of 120 ° C for 10 minutes to initiate the thermal crosslinking treatment. Then, further UV spectra of the samples were recorded. The samples were then cured in ultraviolet light using a 2 X 120 W / cm medium pressure mercury lamp at a tape rate of 5 meters / minute. The absorbance of the sample after flash evaporation corresponds to 100%. The difference between the two spectra after flash evaporation and after 10 thermal cross-links corresponds to the percentage loss of the photoinitiator due to volatility or lack of inclusion. The results can be seen in Table 1. Table 1 Example 9 10 11 12 13 14 Component A 65.19 65.19 65.19 65.19 65.19 65.19 Component B 31.07 31.07 23.8 23.8 26.2 26.2 Starter of Example 1.67 Starter of Example 2 2.95 Starter of Example 3 2.95 Example Starter of 6 2.95 Starter of Example 4 2.59 Starter of Example 5 2.59 Volatility% 0 0 0 0 2.1 1.1 All samples exhibited no or little loss of photoinitiator, indicating the photoinitiator loss. Optimally incorporated in the formulation to be cured, and the photoinitiator 15 did not release from the formulation during the heat treatment. 0 Continued pages (If the description page of the invention is not enough, please note and use the continued page) 72 200305582 玖 、 Explanation of the invention L diagram brief description] None [The main components of the diagram represent the symbol table] None 73

Claims (1)

200305582 Scope of patent application 1 · A combinable photoinitiator compound of formula I, Y is C3-C12 alkynyl, butylene, alkynyl, or C4-C12 alkynyl interrupted one or more times with non-continuous -0 or -NR2- CH— CHj- —ch, i, —CH. 5 Phenyl, cyclohexyl or R! Is selected from OH, SH, NR3R4,-(CO) -OH,-(CO) -NH2, so3h, -C (R5) = CR6R7, ethylene oxide, -0- (C0) -NH-R8-NC0 and -o- (co) -r9- (co) -x reactive groups; R2 is hydrogen, CVC4 alkyl or c2- c4 hydroxyalkyl; each of R and R4 is hydrogen individually, crc4 alkyl or c2-c4 hydroxyalkyl; each of R5, R6 and R7 is hydrogen or methyl individually; 1 ^ 8 is linear or branched c4-c12 alkylene, phenylene, methyl-phenylene, cyclohexanediyl, isophoronediyl, 15 • CH CH; • CH CH— 13 Continued pages (Please note and use the continuation pages when the patent application page is not enough.) 74 200305582 Pick up and apply for the patent application 0 0 II II ^ CH2) 6-NCNCN- (CH2) 6-N = C = 0: (9H2) 6 i? Ίϊ 0 0 ~ iCH2) 6a-g- (CH2) 6-j ^ -0- (〇CH2CH2) i〇〇C ~ ^^, (? H2) 6 Vn / (CH2) 6_ -(ch2) 6-n > = 0 〇 (ch2) 「n = c = 〇5 WCH2)」-(ch2) 6-n > = 0i? WM / = \ (CH2) 6-NC— (0CH2CH2 ) 2-0 " C " C-^^ o or 〇 (c c- (oanyo N R9 is linear or branched CrC16 alkylene, -CH = CH-, -CH = CH-CH2-, C6-cycloalkylene, phenylene, naphthyl, norbornene-5,6-di base, -CH = C- or ch3 o 11 _ H2 CNC 12 H cI and each of X, Xi, and X2 is an OH, Cl, OCH3 or OC2H5. (Use continuation sheet) 75 200305582 fe, patent application range 0 2 · Conjugative photoinitiator compounds of chemical formula I as described in item 1 of the patent application range, wherein R ^ OH. 3. The compound of the incorporable photoinitiator 5 of formula I as described in item 1 of the scope of patent application, wherein Y is a non-continuous -0- discontinuous C4-Ci2 extension base; R ! Is a reactive group selected from 0H, ethylene oxide and -〇_ (CO) -NH-R8-NCO; and? CO ·. Rs is a CHj o 11 CH ο II CN =) 6- Η c T NH " -c-H2) e N—c— I (Me i NH P 'LH IN—c— I, one 1 NH H2) ec 〕 HC NH 9 o = -co = c-0- 2 H C2 CH (0 〇, / (CH2) 6 — (ch2) 6-n > = 0 0 (CH2) jN = C = 0 0 / (CH2 ) "— (Ch2) 6-n > = 〇 or 0 (CH2) 6 ^ NC— (OCH2CH2) j〇-CCH ^^ 0 Continuation page (If the patent application page is not enough, please note and use the continuation Page) 76 200305582 Pick up and apply for patent scope 0 meaning 2/6 _ (CH2) "NN— (CH2) (ϊ 〇 4 · a method of manufacturing a compound of chemical formula ι, wherein r ^ |, 〇h, including the use of phenyl Glyoxylic acid monoester Π f \ J II 10-r (II), where R is q-C4 alkyl, especially methyl or ethyl, reacts with glycol III ho, y-〇h (III) , Where y is as defined in item 范围 of the scope of the patent application, where as catalysts are lithium acetate, sodium acetate, potassium acetate, 10 mg acetic acid, barium acetate, zinc acetate, cadmium acetate, copper (II) acetate, II), aluminum acetate, calcium oxide, lithium methoxide, sodium methoxide, titanium tetraisopropoxide, aluminum triisopropoxide, third butyl Lithium alkoxide, 4 · (dimethylamino) pyridine, or dibutyltin diacetate. 5 · The compound of the formula 所述 described in item ϊ of the patent application scope, wherein Ri 15 is 0H ′, which can be used to manufacture it. The starting material of the initiator has a center of SH, NH,-((:: 0) -0,-(c0) -NH2, s〇3H, 5) = 〇: 11 and ,-(^ (COhNH-RrNCO or; and R3, R4, R5, R6, r7, R8, R9, and X are based on the scope of the first patent application scope. 2 0 6 · A manufacturing as the scope of the patent application scope ϊ The method for the incorporation of a photoinitiator of the chemical formula I described in item 1, wherein, as described in item 1 of the scope of patent application, its 0 continuation page (when the page of the patent application is not enough, please remember the fiber page) 77 200305582 The compounds of the formula I of Ri-OH in the scope of patent application are reacted with isocyanate, carbamoyl chloride, thioisocyanate, acid chloride, acid ester, acid anhydride, chloroformate or epichlorohydrin. 7. A photopolymerizable composition comprising (a) at least one ethylenically unsaturated photopolymerizable compound, and (b) at least as photoinitiator Please compound patentable scope of the first term of the formula I of. 8. The composition as described in item 7 of the scope of patent application, which, in addition to the component (b), further comprises a starter (c) and / or an additive (d). 10 9. The composition according to item 8 of the scope of patent application, wherein the additional light initiator (c) is a compound of formula VIII, IX, X, XI or / and XII ^ 25 (VIII), Ο Ο II II R34Tc-R35 (x) 'Κ33 15 ^ 36 R39-1 " i-R37 (XI), ruler 38 -o-Yro-cc- ^ (XII), of which 0 continued pages (Patent application page When not enough, please note and use the continuation page) 78 200305582 Pick up and apply for patent scope-OCH2CH2-OR29, R25 series hydrogen, C "c18 alkyl, c" Ci8 ^ oxy, morpholino, SCH3 or g4 CH, -ch2-c- • G2 Lc% 27 group R 28 n is 2 to 10; each of 5 Gi and G2 is an end group of a polymer unit, especially hydrogen or CH3; R26 is hydroxyl, CVCU alkoxy, morpholino, di Fluorenylamino or alkyl; each of H7 and R28 is independently hydrogen, Ci_C6 alkyl, phenyl, benzyl, allyl, C1-C16 alkyl, or R27 and R28 and Forms a cyclohexyl ring with the carbon atom to which it is bonded; m is a number from 1 to 20; wherein R26, Rn and Hu are not all CrCb alkoxy or -CKCHzCI ^ COm-CVCw: ^ group; and ff 9 ch3 15 R29 is hydrogen, —C—CH = CH2 or —c—c = ch2 · R30 and R32 are each individually hydrogen or methyl; Rm is hydrogen, methyl, 2-hydroxyethylthio, or phenylthio Phenyl ring of phenylthio group is unsubstituted or substituted with crc4 alkyl group at 4_, 2_, 2,4-, or 2,4,6-position; each of ^ 33 and rule 34 is individually crc20 Alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl, or biphenyl, these groups are unsubstituted or substituted with halogen, cvCu alkyl or / and even alkoxy, or r33 contains s • Or 0 continuation pages (inapplicable patent pages are inadequate, please note and Class) 79/200305582, N-% of the scope of application for patents or heterocycles of heart members or 〇II —c-R35 R3S is hexyl, cyclopentyl, benzyl, naphthyl or biphenyl, these groups are not Substituted or substituted with-or more oxines, c "c4 alkyl groups and / or c" aryloxy substituents, or r35 is a heterocyclic ring containing 5 or 6 members of 3 or N-; Each of 36 and 37 is a cyclopentadienyl group, which is unsubstituted or = alkyl, Ci_Cis alkoxy, cyclopentyl, cyclohexyl, or mono-, di-, or tri-substituted ; And 10 15 38 and R39 are each a benzyl group, and at least one of the positions adjacent to the titanium-carbon bond is substituted with a fluorine atom or CF3, and they may contain as an aromatic ring Further substituents of pyrrolinyl or polyoxaalkyl, each of which is unsubstituted or di- or di-Ci_Ci2 alkyl, bis (CrCi2 alkyl) aminomethyl, morphinylmethyl, c2.c4 Group, methoxymethyl, ethoxymethyl, trimethylmethyl, methyl, methoxy or phenyl, Or R28 and 1139 or R40, R41 and R42 each is hydrogen, halogen, c2_c12 alkenyl, Ci-Cu alkoxy, alkoxy interrupted by one to four oxygen atoms, cyclohexyloxy, Cyclopentyloxy, phenoxy, benzyloxy, unsubstituted or substituted with "(: 4alkoxy-, halo-, phenylthio- or crC4 alkylthio- Phenyl or biphenyl, 0 continuation pages (please note and use continuation pages when the patent application page is insufficient, 80 200305582, where both the ruler 40 and R42 are both hydrogen, and are in " 1 = N at least one R4. Or R42 is Ci-Cu alkoxy, C2-CU alkoxy interrupted by one to four oxygen atoms, cyclohexyloxy, cyclopentyloxy, phenoxy5 or benzyl Oxygen; E1 is 0, S or NR43; R43 is alkyl, phenyl or cyclohexyl; and γι is dialkyl, butyryl, butynyl, or non-continuous or -NR44 * · intermittent one or more Secondly, CrCu alkylene, or hydrazine 10 phenyl, cyclohexyl, CHr or R44 series gas, C1-C4 alkyl or Cz-Cdjji alkyl. 10. The composition according to item 7 of the scope of patent application for Shenyang, in addition to the photochemical curing component, it also contains a heat-curable component. 15 11. The compound of formula I as described in item 1 of the scope of patent application, as a non-volatile monomer, an agglomerated or polymerized compound having at least one ethylenically unsaturated double bond by 200 to 600 nm Photoinitiator for photopolymerization by irradiation with light in the wavelength range. 12. The composition as described in item 7 of the scope of patent application, which is used to manufacture 20 colored and uncolored surface coating compositions, printing inks, screen printing inks, offset printing inks, rubbers Ink and powder coating for printing plate rotation 0 Continued pages (Notes and use of continuation pages when the patent application page is insufficient, 200305582 Pick up and apply for patent applications, printing plates, adhesives, dental composition, Optical wave guide, optical switch, color test system, composite material, glass fiber cable coating, screen printing engraved template, resistive material, color filter, gel coating (thin layer), used in Packaging of electrical and electronic components, manufacturing of magnetic recording materials, 5 Manufacturing of three-dimensional objects by stereolithography, photocopying, image recording materials, especially holographic recording, manufacturing decoloring materials, especially for image recording materials Color materials, or to make micro-capsule image recording materials. ^ 13. A coated substrate that is coated on at least one 10 ^ ^ from a composition as described in claim 7 of the patent application. 82 200305582 Lu, (a), the designated representative of the case is: Figure _ (b), the representative symbols of the representative diagram are briefly explained: 柒, if there is a chemical formula in this case, please reveal the chemical formula that can best show the characteristics of the invention: II 0, / 〇 一 · Υ 一 RC 1 II 〇 4